GIDW Virtual Poster Competition Program 2020

New self-assembled hetero-metallomacrocycles as biomolecular probes and therapeutics

Stephen Opeyemi Aderinto
@AderintoStephen (https://twitter.com/AderintoStephen)
Graduate Student at University of Sheffield, Sheffield, United Kingdom

Jim Thomas, University of Sheffield, United Kingdom

Abstract:

The ability of self-assembled, kinetically-inert, water-soluble homo- and hetero- metallomacrocycles constructed from kinetically-inert d6-cations and possessing highly-structured binding pockets made up of hydrophobic aromatic residues to bind DNA in biologically-relevant conditions has been explored, leading to the synthesis of Complex 1, the first-ever reported tetranuclear RuII2ReI2, heteroleptic polypyridyl complex, which functions as a DNA-targeting sensitizer for PDT.

References, if applicable:

1. (a) Fujita, M.; Tominaga, M., Hori A., Therrien, B. Acc. Chem. Res. 2005, 38, 369. (b) Thomas, J. A. Chem. Soc. Rev. 2007, 36, 856. (c) Chakrabarty, R.; Mukherjee, P. S.; Stang, P. J. Chem. Rev. 2011, 111(11), 6810. (e) Thomas, J. A. Dalton Trans. 2011, 40, 12005.
2. (a) de Wolf, P.; Heath, S. L.; Thomas, J. A. Chem. Commun. 2002, 2540. (b) de Wolf, P.; Waywell, P.; Hanson, M.; Heath, S. L.; Meijer, A. J. H. M.; Teat, S. J.; Thomas, J. A. Chem. Eur. J. 2006, 12, 2188.
3. (a) Ghosh, D.; Ahmad, H.; Thomas, J. A. Chem. Commun. 2009, 2947. (b) Ahmad H.; Hazel, B. W.; Meijer, A. J. H. M.; Thomas, J. A.; Wilkinson, K. A. Chem. Eur. J. 2013, 19, 5081. (c) Ahmad, H.; Ghosh, D.; Thomas, J. A. Chem. Commun. 2014, 50, 3859.
4. Walker, M. G.; Jarman, P. J.; Gill, M. R.; Tian, X.; Ahmad, H.; Reddy, P. A. N.; McKenzie, L.; Weinstein, J. A.; Meijer, A. J. H. M.; Battaglia, G.; Smythe, C. G. W.; Thomas, J. A. Chem. Eur. J. 2016, 22(17), 5996.
5. Allison, R. R.; Sibata, C. H. Photodiagn. Photodyn. Ther. 2010, 7(2), 61.

Exploring New Reaction Partners Towards the Activation Phosphine Gas (PH3(g)))

Jeanette A. Adjei
@jeanette_adjei (https://twitter.com/jeanette_adjei)
Graduate Student at Western University, London, Canada

Paul Ragogna, Western University, Canada; Michael Kerr, Western University, Canada

Abstract:

This project aims to expand the scope of PH3 chemistry towards the synthesis of new and valuable organophosphorus compounds for use in catalysis and metal coordination. Hydrophosphination reactions were used to explore the ringing opening of vinylcycloprapane and the P-H bond addition of commercially available natural products. Primary and secondary phosphines were initially used to develop the methodology of these reactions before exploring the activation of PH3.

References, if applicable:

1. Svara, J; Weferling, N; Hofmann, T. In Ullman’s Encyclopedia of Industrial Chemistry; Wiley-VCH: Weinhem, 2012; Vol. 27, pp 19-49.
2. Guterman, R.; Gillies, E. R.; Ragogna, P. J. Dalton Trans., 2015, 44, 15664.
3. Beland, V. A.; Ragogna, P. J. ACS Appl. Mater. Interfaces, 2020, XXX, XXXX.
4. Irwin, L. Cl; Renwick, C. R.; Kerr, M. A. J.Org. Chem., 2018, 83, 6235.
5. Robertson, A.; Bradaric, C.; Frampton, C. S; McNulty, J.; Capretta, Al., 2001, 42, 2609.

Synthesis, characterisation and properties of  tris(3,5-difluorophenyl)borane

Mashael  Alharbi
@Mashaelmusaad (https://twitter.com/Mashaelmusaad)
Graduate Student at Cardiff University, Cardiff, United Kingdom

Dr.Rebecca Melen

Abstract:

Due to extensive applications of Lewis acid boranes such as B(C6F5)3, this work intends to synthesize novel Lewis acidic compounds.1 These will be explored in a wide range of reactions, including small molecule activation and frustrated Lewis pair catalysis. Tris(3,5-difluorophenyl)borane has been synthesized and characterized by multinuclear NMR, mass spectroscopy, and XRD. The Lewis acidity has been determined using both the Gutmann Beckett method and the Childs’ method.

References, if applicable:

1- Beckett, M. A.; Brassington, D. S.; Coles, S. J.; Hursthouse, M. B. Inorg. Chem. Comm. 2000, 3, 530-533.

 2- Jacobsen, H.; Berke, H.; Doring, S.; Kehr, G.; Erker, G.; Frohlich, R.; Meyer, O. Organometallics, 1999, 18, 1724-1735.

 3- Chase, P. A.; Welch, G. C.; Jurca, T.; Stephan, D. W. Angew. Chem., Int. Ed. 2007, 46, 8050-8053.

 4- Ménard, G.; Stephan, D. W. J. Am. Chem. Soc. 2010, 132, 1796-1797.

The role of porphyrin peripheral substituents in determining the reactivities of ferrous nitrosyl species

Sk  Amanullah
@SkAmanullah (https://twitter.com/SkAmanullah)
Graduate Student at Indian Association for the Cultivation of Science, Kolkata, India

Paramita Saha, Indian Association for the Cultivation of Science, India; Abhishek Dey, Indian Association for the Cultivation of Science, India

Abstract:

{FeNO}7 is an intermediate common to the catalytic cycles of Cd1NiR(nitrite to NO) and CcNiR(nitrite to NH4+), heme-based NiRs, and its reactivity varies dramatically in these enzymes.[1,2] A series of iron porphyrinoids, designed to model the electron-withdrawing peripheral substitution as well as the saturation present in heme d1 in Cd1NiR, and their NO adducts were synthesized and their properties were investigated. The detailed analysis explains the difference between PCET vs NO release.[3]

References, if applicable:

1. Averill, B. A. Chem. Rev. 1996, 96 (7), 2951-2964
2. Maia, L. B.; Moura, J. J. G. Chem. Rev. 2014, 114 (10), 5273-5357
3. Amanullah, S.; Dey, A. Chem. Sci. 2020, 11, 5909

Iron Amino-phenolate Complexes for CO2 Activation: Selectivity Control in Ligand Design

Kori A Andrea
koriandrea (http://twitter.com/koriandrea)
Graduate Student at Memorial University, St John’s, Canada

Tyler Brown, Memorial University of Newfoundland, Canada; Erika Butler, Memorial University of Newfoundland, Canada

Abstract:

We have recently reported a collection of iron (III) amino-phenolate complexes active towards the selective production of either cyclic or polycarbonates from epoxides and CO2. Selectivity towards either product was found to be dependent both the nature of the phenolate donor, electronics and coordination geometries. During coupling reactions, those complexes in a square pyramidal geometry undergo an epoxide deoxygenation step leading to the corresponding bridged-oxo species.

References, if applicable:

1. Andrea, K. A.; Brown, T. R.; Murphy, J. N.; Jagota, D.; McKearney, D.; Kozak, C. M.; Kerton, F. M. Inorg. Chem., 2018, 57, 13494-13504.
2. Andrea, K. A.; Butler, E. D.; Brown, T. R.; Anderson, T. S.; Jagota, D.; Rose, C.; Lee, E. M.; Goulding, S. D.; Murphy, J. N.; Kerton, F. M.; Kozak, C. M.; Inorg. Chem., 2019, 58, 11231-11240.

Unexpected Reactivity of Structurally Diverse, Neutral,  Hypervalent P Compounds

Nayanthara  Asok
@NayantharaAsok (https://twitter.com/NayantharaAsok)
Graduate Student at York University, Toronto, Canada

Dr. Joshua Gaffen, York University, Canada. Dr. Ekadashi Pradhan, York University, Canada. Dr. Toby Zeng, York University, Canada. Dr. Thomas Baumgartner, York University, Canada.

Abstract:

Dithienophospholes provide an interesting conjugated framework towards the synthesis of neutral pentavalent phosphorus compounds with FLP characteristics. These hypervalent compounds acquire a square pyramidal structure that is highly unusual for pentavalent phosphorus species. This peculiar geometry imparts interesting chemical properties that will be highlighted in this contribution.

References, if applicable:

1. Baumgartner, T. Insights on the Design and Electron-Acceptor Properties of Conjugated Organophosphorus Materials. Acc. Chem. Res. 2014, 47, 1613.
2. Green, M. L. H.; Parkin, G. The classification and representation of main group element compounds that feature three-center four-electron interactions. Dalton Trans. 2016, 45, 18784.
3. Osman, F.H.; El-Samahy, F. A. Reactions of α-Diketones and o-Quinones with Phosphorus Compounds. Chem. Rev. 2002, 102, 629.
4. Baumgartner, T.; Neumann, T.; Wirges. B. The Dithieno[3,2-b:2’,3’-d]phosphole System: A Novel Building Block for Highly Luminescent π-Conjugated Materials. Angew. Chem. Int. Ed. 2004, 43, 6197.
5. Ren, Y.; Dienes, Y.; Hettel, S.; Parvez, M.; Hoge, B.; Baumgartner, T. Highly Fluorinated Dithieno[3,2-b:2′,3′-d]phospholes with Stabilized LUMO Levels. Organometallics 2009, 28, 734.
6. Marczenko, K. M.; Zurakowski, J. A.; Kindervater, M. B,; Jee, S.; Hynes, T.; Roberts, N.; Park, S.; Werner-Zwanziger, U.; Lumsden, M.; Langelaan, D. N.; Chitnis, S. S. Periodicity in Structure, Bonding, and Reactivity for p-Block Complexes of a Geometry Constraining Triamide Ligand. Chem. Eur. J. 2019, 25, 16414.
7. Maskey, R.; Schädler, M.; Legler, C.; Greb, L. Bis(perchlorocatecholato)silane – A Neutral Silicon Lewis Super Acid. Angew .Chem. Int. Ed. 2018, 57, 1717.
8. Greb. L. Lewis Superacids: Classifications, Candidates, and Applications. Chem. Eur. J. 2018, 24, 17881.

Photocatalytic degradation of 2,4 Dichlorophenol by the Nickel Zinc ferrite graphene oxide nanocomposite

Collen  Bapiro
@firebapiro (https://twitter.com/firebapiro)
Undergraduate Student at Midlands State University, Harare, Zimbabwe

Abstract:

The widespread use of chemicals in manufacturing industries and their frequent release into the environment is the major cause of pollution, worldwide. Inorganic chemistry can be used to synthesize compounds that degrade water pollutants.

References, if applicable:

Electrochemistry and NMR Experiments of Reactions Containing Nickel(II) Complexes and CO2 in Methanol

Zaira J Barrera
@zjbarrera (https://twitter.com/zjbarrera)
Undergraduate Student at University of California, Irvine, Irvine, USA

Jenny Yang, University of California, Irvine, USA

Abstract:

Reducing CO2 to formate is a way to recycle it into a sustainable fuel. NMR and CV experiments were conducted to observe the reactivity of [Ni(dmpe)2][PF6]2 & to see if [HNi(dmpe)2][PF6] reacts with CO2 to produce formate in MeOH. Formate was seen at 8.5 ppm after adding CO2 to the Ni hydride. Moreover, CV experiments with [Ni(dmpe)2][PF6]2 under N2 revealed that at low scan rates, irreversible formation of the Ni hydride occurred. At high scan rates, a return of the Ni(II/0) peak was observed.

References, if applicable:

1) Miedaner, A.; DuBois, D. L.; Curtis, C. J.; Haltiwanger, R. C. Organometallics 1993, 12 (2), 299-303.

2) Tsay, C.; Livesay, B. N.; Ruelas, S.; Yang, J. Y. J. Am. Chem. Soc. 2015, 137, 44, 14114-14121.

Polynuclear Lanthanide-Diketonato Clusters: Catalytic Hydroboration of Carboxamides and Esters

Deepika  Bedi
@deepika2705 (https://twitter.com/deepika2705)
Graduate Student at Texas Tech University, Lubbock, USA

Abstract:

Catalytic reduction of carboxamides into their corresponding amines is an attractive but extremely challenging transformation. We have shown the direct deoxygenation of carboxamides using earth-abundant lanthanum catalysts in the presence of HBpin, delivers good to excellent yields of amines. The reaction was screened for a myriad of substrates and shows excellent functional group tolerance. Furthermore, this strategy was successfully employed to a broad range of esters.

References, if applicable:

Umpolung of P-H Bond Activation for Hydrophosphination

Roman G Belli
@belli_roman (https://twitter.com/belli_roman)
Post-doctoral Fellow at University of Minnesota, , USA

Carly Slusar (University of Victoria, Canada), Hayley Parkin (University of Victoria, Canada), Dimitrios A. Pantazis (Max-Planck-Institut für Kohlenforschung, Germany), Robert McDonald (University of Alberta, Canada), Lisa Rosenberg (University of Victoria, Canada)

Abstract:

Efforts to develop a hydrophosphination catalyst system based on complexes that contain phosphenium ligands is described. A key step in this proposed novel catalysis is activation of a P–H bond via hydride abstraction, which we utilized to prepare phosphenium complexes from their respective secondary phosphine precursors. The viability of the additional steps for this proposed catalysis, electrophilic P-C bond formation and hydride transfer, are demonstrated even for substrates such as ethylene.

References, if applicable:

Pushing the Lewis Acidity Boundaries of Boron Compounds With Non-Planar Triarylboranes Derived from Triptycenes

Ali  BEN SAIDA
@Dr_Berionni (https://twitter.com/dr_berionni?lang=fr)
Graduate Student at University of Namur, Namur, Belgium

Guillaume Berionni, University of Namur, Belgium

Abstract:

Bending the archetypal planar trigonal boron atom environment of triarylboranes results in exceptional enhancement of the boron Lewis acidity without requiring electron-withdrawing groups.

The bora-phosphatriptycene, which we found to be one of the strongest Lewis acids known up to date and which showed promising reactivities for activating carbon-halogen bonds [1]. This bifunctional Lewis acid-base compounds allow the formation of new polymer material.

References, if applicable:

1. Ben Saida, A., Chardon, A., Osi, A., Tumanow, N., Wouters, J., Adjieufack, A., Champagne, B., Berionni, G. Angew. Chem. Int. Ed., 2019, 58, 16889.

Fluorescent Lewis Adducts: A Practical Guide to Relative Lewis Acidity

Jordan N Bentley
@BoronBentley (https://twitter.com/BoronBentley)
Graduate Student at York University, Toronto, Canada

Amy Laturski, Seja Elgadi, Joshua Gaffen, Paul Demay-Drouhard, Thomas Baumgartner, Christopher Caputo, Department of Chemistry, York University, 4700 Keele Street, Toronto, ON M3J 1P3, Canada

Abstract:

Recently, we developed a new fluorescence-based method to evaluate the acidity of a series of Lewis acids across the p- and d-blocks of the periodic table with great precision. We have now considerably expanded the scope of the Fluorescent Lewis Adduct (FLA) method by systematically investigating the strength of over 50 Lewis acids in toluene; some of which have never been experimentally measured before.

References, if applicable:

(1) Gaffen, J. R.; Bentley, J. N.; Torres, L. C.; Chu, C.; Baumgartner, T.; Caputo, C. B. Chem 2019, 5, 1567–1583.

Triple Decker Sandwich Complexes Containing Six Membered Ring

Moulika  Bhattacharyya
@bhatt_mou (https://twitter.com/bhatt_mou)
Post-doctoral Fellow at University of Windsor, Windsor, ON, Canada, Canada

Abstract:

Compounds containing flat ring made of boron are very rare and only a handful of such compounds are known. Recently, we have isolated various triple-decker sandwich complexes containing puckered to flat middle rings composed of boron and non-boron elements. The complexes show 22-24-valence electrons that represent the lowest electron count triple-decker complexes. The key results of this work will be described.

References, if applicable:

[1] (a) Greenwood, N. N. Earnshaw, A.; Chemistry of the Elements; 2nd ed.;

Butterworth-Heinemann: Oxford, 1997.

[2] (a) Grimes R. N. Carboranes, 2nd ed.; Academic Press: London, 2011 (b) Grimes, R.

4. J. Organomet. Chem. 2013, 747, 4.

[3] (a) Thakur, A.; Chakrahari, K. K. V.; Mondal, B.; Ghosh, S. Inorg. Chem. 2013, 52,

2262; (b) Mondal, B.; Mondal, B.; Pal, K.; Varghese, B.; Ghosh, S. Chem.Commun.

2015, 51, 3828; (c) Mondal, B.; Bhattacharyya, M.; Varghese, B.; Ghosh, S. Dalton

Trans. 2016, 45, 10999.

[4] (a) Lauher, J. W.; Elian, M.; Summerville, R. H.; Hoffmann, R. J. Am. Chem. Soc.

1976, 98, 3219; (b) Jemmis, E. D.; Reddy, A. C. J. Am. Chem. Soc. 1990, 112, 722.

(c) Jemmis, E. D.; Reddy, A. C. Organometallics 1988, 7, 1561.

Synthesis and Reactivity of a Hypersilylsilylene

Milan Kumar Bisai
@BisaiMilan (https://twitter.com/BisaiMilan)
Graduate Student at CSIR-NCL Pune, Pune, India

Dr. Sakya S. Sen, Principal Scientist, Catalysis & Inorganic Chemistry Division, CSIR-National Chemical Laboratory, INDIA

Abstract:

Stabilization of an amidinatosilylene with a bulky hypersilyl substituent was realized with the preparation of PhC(NtBu)2Si{Si(SiMe3)3} in more than 90% yield. Subsequent to the synthesis of the silylene, we studied its reactivity toward Me3NO, S, Se, and Te. Silaoxirane formation was observed when it was treated with acetone. Formation of tetraphosphilosilane was also realized by the reaction of chlorodiphenylphospine.

References, if applicable:

1. Bisai, M. K.; Swamy, V. S. V. S. N.; Das, T.; Vanka, K.; Gonnade, R. G.; Sen, S. S. Inorg. Chem. 2019, 58, 10536.

Investigating coordination tendencies of low valent Ti(III) and V(II)

Hannah R Bloomfield
@slowlydiene (https://twitter.com/slowlydiene)
Undergraduate Student at The University of Winnipeg, Winnipeg, Canada

Jamie Ritch, The University of Winnipeg, Canada

Abstract:

Low oxidation state transition metals (Ti3+/V2+) are underexplored compared to more stable oxidation states (Ti4+/V3+). We theorized that the strong σ-donating and p-accepting ability of NHCs may render them good spectator ligands for these low valent metals. Various NHCs were reacted with VCl2(TMEDA)2 and TiCl3(THF)3 to study coordination tendencies, complemented by DFT calculations. This poster will highlight our experimental and computational efforts to identify ideal NHCs for stabilization.

References, if applicable:

Synthesis of iron nitrosyl complexes with diethyldithiocarbamate ligands

Evan F Bonnand
@Evan_Bonnand (https://twitter.com/Evan_Bonnand)
Undergraduate Student at Cal Poly Pomona, , USA

Dr.  Chantal Stieber, CPP, USA

Abstract:

Literature reports the formation of an iron nitrosyl complex first, followed by the coordination of two dtc ligands. This work explores that approach by varying stoichiometric ratios and types of reagents used with the goal of optimizing reaction conditions and establishing an air-stable synthetic method. Deviations from literature include using FeIII instead of FeII with both silver and sodium dtc salts. IR and NMR spectroscopy were utilized to verify the formation of the complex.

References, if applicable:

(1) Additional Materials for the Iron Nitrosyl experiment http://www.chem.ucla.edu/~bacher/CHEM174/hints/Iron_Nitrosyl.html (accessed Jun 30, 2020).

(2) Iron Nitrosyl compounds www.chem.ucla.edu/~bacher/CHEM174/Lectures/…Nitrosyl.pptx (accessed Jun 30, 2020).

The Phospha-Bora-Wittig Reaction

Andryj  Borys
@AndryjBorys (https://twitter.com/AndryjBorys)
Post-doctoral Fellow at University of Edinburgh, Edinburgh, Scotland

Ella F. Rice, University of Edinburgh, Scotland; Gary S. Nichol, University of Edinburgh, Scotland; Michael J. Cowley, University of Edinburgh, Scotland.

Abstract:

Transient phosphaborenes, [Mes*P=B-NR₂], undergo a [2+2] cycloaddition with aldehydes and ketones to give 1,2,3-phosphaboraoxetanes, which can be converted into phosphaalkenes using sub-stoichiometric N-heterocyclic carbene or AlBr₃, with loss of [R₂N-BO]₃. In contrast, phosphaalkenes are directly prepared from esters and amides, offering a versatile method for transforming carbonyl compounds into phosphaalkenes via the ‘phospha-bora Wittig’ reaction.

References, if applicable:

Birch Bark-Oil (Maskwiomin): Synthesis and Analysis of an L’nu Indigenous Skin Ointment

Sarah Mary Margaret Boudreau
@BoudreauChem (https://twitter.com/BoudreauChem)
Undergraduate Student at Cape Breton University, Sydney, Canada

Raj Kalia, Cape Breton University, Sydney, NS, Canada; David Irwin, Cape Breton University, Sydney, NS, Canada; Tuma Young, Cape Breton University, Sydney, NS, Canada; Matthias Bierenstiel, Cape Breton University, Sydney, NS, Canada

Abstract:

Maskwiomin (birch bark-oil) is an almost forgotten L’nu medicine for the topical treatment of skin conditions (psoriasis, eczema, rashes). The L’nu method of producing the oil involves torrefaction in a campfire using a can-over-can process. The Bierenstiel group has been developing a process to control the conditions of this process with an electrical and temperature-controlled reactor. The goal of this project is to modify the conditions of the reactor to obtain better, reproducible results.

References, if applicable:

1. Flechter, O. B.; et al. Pharm. Chem. J. 2005, 39, 401-404.
2. Jager, S.; et al. Molecules 2008, 13, 3224-3235.
3. Krasutsky, P. A. Nat. Prod. Rep. 2006, 23, 919-942.

New Chemistry of Copper Halides: Alkyl C-H Fluorination and N/O/S-Nitrosation

Jamey  Bower
@notJamey (https://twitter.com/notJamey)
Graduate Student at The Ohio State University, Columbus, United States of America

Shiyu Zhang

Abstract:

New copper halide complexes are presented that perform alkyl C-H fluorination and N/O/S-nitrosation enabled by highly covalent metal-ligand interactions. The complexes are best described as copper(II) antiferromagnetically coupled to a ligand-centered radical, which provides key insights into their reactivity. Together, these studies highlight the synergy between multireference electronic structures and ligand-centered radical reactivity of copper complexes with ambiguous oxidation states.

References, if applicable:

1. Bower, J. K.; Cypcar, A. D.; Henriquez, B.; Stieber, S. C. E.; Zhang, S. J. Am. Chem. Soc. 2020, 142, 8514.
2. Bower, J. K.; Sokolov, A. Yu.; Zhang, S. Angew. Chem. Int. Ed. 2019, 58, 10225.

Self-assembly of nanoparticles in emulsion: a green approach to produce functional silica composites

David F.F. Brossault
@BrossaultDavid (https://twitter.com/BrossaultDavid)
Graduate Student at University of Cambridge, Cambridge, United Kingdom

Alexander Routh, University of Cambridge, UK

Abstract:

Silica composites are promising materials, used for biological and environmental applications. However, their preparation is often time-consuming and requires toxic chemicals or high temperatures. This poster presents a green approach to produce metal doped silica composites at room temperature via salt-induced assembly of nanoparticles in aqueous droplets.[1] Such a method is fast, tuneable and can easily be adapted to produce functional systems (e.g Recoverable Photocatalytic Microbeads).[2]

References, if applicable:

1. Brossault, D.; Routh, A. J. Colloid Interface Sci. 2020, 562, 381.
2. Brossault, D.; McCoy, T.; Routh, A. Manuscript under review

Nanocomposites and their recent advancements

Pavan  C
@pavan_1998 (https://mobile.twitter.com/pavan_1998)
Undergraduate Student at Acharya and BM Reddy College of Pharmacy, Bangalore, India

Madhavi BLR, Professor, India

Abstract:

Nanocomposites are versatile in their applications such as anti-corrosive, healing of bones, sensors, environmental protection, packaging, wastewater treatment, and diagnosis of tumors. Adverse effects are not just due to their individual properties of components but influence their morphology, dispersion, and interfacial characteristics. Advancements of nanocomposites are the production of flexible and rigid packaging and nanofillers creating nanocomposite structures with improved properties.

References, if applicable:

A DFT and Experimental Investigation of the Ring Stability of Thionylphosphazenes

Rachele Nicole Carafa
@rachcara23 (https://twitter.com/rachcara23)
Graduate Student at Ryerson University, Toronto, Canada

1. Stephen Wylie, Ryerson University, Canada; Daniel A. Foucher, Ryerson University, Canada; Andrew R. McWilliams, Ryerson University, Canada

Abstract:

Thionylphosphazenes have been shown to undergo ring-opening polymerization (ROP) at both elevated temperatures in the melt and at ambient temperatures in the presence of Lewis acids, but the mechanism on how this works is not fully understood. This study aims to apply novel DFT calculations to thionylphosphazenes and some of its derivatives to update current literature calculations while also providing more insight into their ring stability and the ROP mechanism.

References, if applicable:

McWilliams, A. R.; Gates, D. P.; Edwards, M.; Liable-sands, L. M.; Guzei, I.; Rheingold, A. L.; Manners, I.; April, R. V. Reaction of the Cyclic Thionylphosphazene NSOCl[NPCl2]2 with Halide Abstraction Agents: An Ambient Temperature Ring-Opening Polymerization (ROP) Route to Poly(Thionylphosphazenes). J. Am. Chem. Soc. 2000, 122 (6), 8848–8855.

Unlocking the catalytic potential of  tris(3,4,5-trifluorophenyl)borane using microwave irradiation

Jamie  Carden
jamie_carden (https://twitter.com/jamie_carden)
Graduate Student at Cardiff University, Cardiff, United Kingdom

Lukas Gierlichs, Cardiff University, UK. Duncan F. Wass, Cardiff University, UK. Duncan L. Browne, Cardiff University and University College London, UK, Rebecca L. Melen, Cardiff University, UK

Abstract:

In this work we explore the catalytic properties of tris(3,4,5-trifluorophenyl)borane towards hydroboration, and the use of microwave irradiation to allow conventionally difficult hydroboration reactions to occur

References, if applicable:

Carden J. L, Gierlichs L. J., Wass D. F., Browne D. L., and Melen R. L., Chem. Comm., 2019, 55, 318.

Ligand Field Inversion in Sterically Confined Copper Architectures

Kurtis Mickel Carsch
@kcarsch (https://twitter.com/kcarsch)
Graduate Student at Harvard University, Somerville, United States

Ida M. DiMucci, Cornell University, USA. Kyle M. Lancaster, Cornell University, USA. Theodore A. Betley, Harvard University, USA

Abstract:

The isolation and characterization of formally high-valent Cu(III) complexes permits a rigorous disambiguation of electronic structure. We demonstrate ligand field inversion is general in which a physical 3d8 electronic configuration is inaccessible and metal-ligand multiple bonding is attenuated. These findings facilitate refined considerations of how the absence of metal-ligand multiple bonds in late transition metal complexes dictate electronic structure and multi-electron catalysis.

References, if applicable:

1. Carsch, K.M.; DiMucci, I.M.; Iovan, D.A.; Li, A.; Zheng, S.-L.; Titus, C.J.; Lee, S.J.; Irwin, K.D.; Nordlund, D.; Lancaster, K.M.; Betley, T.A. Science 2019, 365, 1138.

2.Carsch, K. M.; Lukens, J. T.; DiMucci, I. M.; Iovan, D. A.; Zheng, S.–L.; Lancaster, K. M.; Betley, T. A. J. Am. Chem. Soc. 2020, 142, 2264.

3. DiMucci, I.M.; Lukens, J.T.; Chatterjee, S.; Carsch, K.M.; Titus, C.J.; Lee, S.J.; Nordlund, D.; Betley, T.A.; MacMillan, S.N.; Lancaster, K.M. J. Am. Chem. Soc. 2019, 141, 18508.

Bis-Ferrocenyl-Pyridinediimine Trinuclear Mixed-Valent Complexes with Metal-Binding Dependent Electronic Coupling

Cole H Carter
coal_carter (https://twitter.com/coal_carter)
Graduate Student at Northwestern University, Evanston, United States

Yosi Kratish, Northwestern University, USA; TItel Jurca, Univeristy of Central Florida, USA; Yanshan Gao, Northwestern University, USA; Tobin marks, Northwestern University, USA;

Abstract:

A family of ferrocene substituted Pyridinediimine metal dichloride (Fc2PDI)MCl2 complexes were synthesized and electronically characterized. While the parent Fc2PDI ligand does not demonstrate electronic coupling between Fc units, metallation with MCl2 ions promotes electronic coupling and delocalization between metals in their mixed valent state. DFT, crystallography, and spectroelectrochemistry aid in gaining granular detail about structural and electronic changes in mixed valent species

References, if applicable:

One ligand, two approach.

Miguel A Chacon Teran
@mchacon233 (https://twitter.com/mchacon233)
Graduate Student at Universidad Simon Bolivar (VE) / Universität Regensburg (DE), Caracas, Venezuela

Miguel A. Chacón‐Terán, Universidad Simon Bolivar, Venezuela; Rafael E. Rodríguez‐Lugo, Instituto Venezolano para Investigaciones Cientificas, Venezuela; Robert Wolf, Universität Regensburg; Vanessa R. Landaeta, Universidad Simon Bolivar, Venezuela.

Abstract:

Recent findings motivate to look forward P(OQuin)3-chemistry. [1] In these sense, two new different P(OQuin)3-approach toward  second row-TM are presented. A P(OQuin)3-Ru system, is a suitable catalyst for the dehydrogenative homo-/heterocoupling of silanes providing a TOF of 6000 h-1. While a P(OQuin)3-Rh system provide an excellent regiocontrol over the dearomative hydroboration of Py and Quin to yield 1,2-dehydroheterocycles under mild condition where additive or base are not required.

References, if applicable:

[1] (a) Rodríguez‐Lugo, R. E.; Chacón‐Terán, M. A.; De León, S.; Vogt, M.; Rosen-thal, A. J.; Landaeta, V. R., Dalton Trans., 2018, 47, 2061. (b) Chacón‐Terán; M. A.; Rodríguez‐Lugo, R. E.; Wolf, R.; Landaeta. V. R., Eur. J. Inorg. Chem, 2019, 39-40, 4336.

Synthesis of Pentasubstituted 2-Aryl Pyrroles from Boryl and Stannyl Alkynes via One-Pot Sequential Ti-Catalyzed [2+2+1] Pyrrole Synthesis/Cross Coupling Reactions

Yukun  Cheng
@YukunCheng1 (https://twitter.com/YukunCheng1)
Graduate Student at University of Minnesota, Minneapolis, United States

Ian Tonks, University of Minnesota, United States

Abstract:

Pyrroles are commonly found in bioactive small molecule scaffolds, yet the synthesis of highly-substituted pyrrole cores remains challenging. Herein, we report a catalytic synthesis of 2-(9-BBN or SnR3) pyrroles via Ti-catalyzed [2+2+1] heterocoupling of heteroatom-substituted alkynes. The resulting 2-boryl substituted pyrroles can be used in Suzuki reactions in a one-pot fashion, resulting in pentasubstituted 2-aryl pyrroles that are inaccessible via previous [2+2+1] heterocoupling strategies.

References, if applicable:

Hydrostibination of acetylenes: a mechanism

Saurabh S. Chitnis
@chitnislab (https://twitter.com/chitnislab)
Academia – Faculty/Staff at Dalhousie University, Halifax, Canada

Josh W. M. MacMillan, Katherine M. Marczenko, Erin R Johnson

Abstract:

Boranes have a low-energy vacant p-orbital and a hydridic B-H bond. This unlocks hydroboration. We have reported stibines, R2SbH, having a low-energy σ* LUMO and hydridic Sb-H bonds, which perform hydrostibination.[1] This poster describes experiments to discover the mechanism of this reaction

References, if applicable:

Marczenko, K. M.; Zurakowski, J. A.; Bamford, K. L.; MacMillan, J. W. M.; Chitnis, S. S. Angew. Chem. Int. Ed., 2019, 58, 18096.

Cobalt PCP Carbene Complexes for the Activation of Small Molecules

Marissa Lorrene Clapson
@Chemrissa (https://twitter.com/Chemrissa)
Graduate Student at University of Calgary, Calgary, Canada

Benjamin Gelfand, University of Calgary, Canada; Jian-Bin Lin, Memorial University, Canada; Warren E. Piers, University of Calgary, Canada

Abstract:

Co(I)-X (X = Cl or Br) PCP carbene complexes can be readily synthesized following treatment of the corresponding tetrahedral Co(II)X2 complexes with NaHBEt3 and Gomberg’s dimer. Treatment of the Co(I)-X complexes with either CsOH or LiCH2TMS, results in the formation of the Co(I)-OH and Co(I)-CH2TMS complexes, respectively. Co(I)-OH, when placed under vacuum, forms a Co(I)-O-Co(I) μ-oxo complex. Exposure of Co(I)-O-Co(I) to CO2 results in the rapid formation of a bridging carboxylate species.

References, if applicable:

(1)          Smith, J. D.; Chih, E.; Piers, W. E.; Spasyuk, D. M. Polyhedron 2018, 155, 281.

(2)          LaPierre, E. A.; Piers, W. E.; Gendy, C. Organometallics 2018, 37 (20), 3394.

(3)          Sung, S.; Wang, Q.; Kraemer, T.; Young, R. D. Chem. Sci. 2018.

(4)          Burford, R. J.; Piers, W. E.; Ess, D. H.; Parvez, M. J. Am. Chem. Soc. 2014, 136 (8), 3256.

Diverse Structure and Reactivity of Pentamethylcyclopentadienyl Antimony (III) Cations

Omar  Coughlin
@CoughlinOmar (https://twitter.com/coughlinomar)
Graduate Student at Nottingham Trent University, Nottingham, United Kingdom

Sophie L. Benjamin, Nottingham Trent University, United Kingdom Tobias Krämer, Maynooth University, Ireland

Abstract:

Heavy Group 15 organometallic complexes are emerging as powerful reagents with the potential to perform specific stoichiometric and catalytic transformations.[1-3]  Harnessing advances in novel synthetic strategies and inspired by recent reports of main group cations with metallocene structures,[4-5] we have synthesised a range of pentamethylcyclopentadienyl antimony(III) cations and probed their diverse structure and reactivity.[6]

References, if applicable:

[1] Planas, O.; Wang, F.; Leutzsch, M.; Cornella, J. Science. 2020, 367, 313.

[2] Stephan, D. W.; Erker, G. Angew. Chem., Int. Ed. 2015, 54, 6400.

[3] Pan, B.; Gabbai, F. P. Angew. Chem., Int. Ed. J. Am. Chem. Soc. 2014, 136, 9564.

[4] Zhou, J.; L. Liu, L.; L. Cao, L.; W. Stephan, D. Chem. 2018, 4, 2699.

[5] N. Jones, J.; H. Cowley. A; L. B. Macdonald, C. Chem. Commun. 2002, 1520.

[6] Coughlin, O.; Krämer, T.; Benjamin, S.L. Dalton Trans. 2020, 49, 1726.

Synthesis and Characterization of Flexible and Rigid Stannane Intermediates & Tin Polymers

Gloria M. D’Amaral
@gloriadamaral (https://twitter.com/gloriadamaral)
Graduate Student at Ryerson University, Toronto, Canada

Daniel Foucher, Ryerson University, Canada

Abstract:

Polystannanes are a unique class of polymers that consist of a backbone of covalently linked tin atoms, however they display an extreme sensitivity to light and moisture. Recently, the Foucher group has demonstrated significant stability improvements when there is an increase in electron density around the tin center via hypercoordination. Using this evidence, my project focuses on synthesizing light and moisture stable polystannanes and exploring their semiconductive properties.

References, if applicable:

1. Pau, J.; D’Amaral, G. M.; Lough, A. J.; Wylie, R. S.; Foucher, D. A. Chem. Eur. J. 2018, 24, 18762–18771.

Facile preparation of a family of {M2Dy} (M= Cu(II), Zn(II)) compounds with rare Dy(III) coordination geometries and SMM behaviour using the “metal complexes as ligands” synthetic approach

Cody  Daneluik
@CodyDaneluik (https://twitter.com/CodyDaneluik)
Undergraduate Student at Brock University, Niagara Falls, Canada

Albert Escuer, Universitat de Barcelona, Spain, Jinkui Tang, Chinese Academy of Sciences, China, Melanie Pilkington, Brock University, Canada, Theocharis C. Stamatatos, University of Patras, Greece

Abstract:

An N3O3 ligand (H3L) was employed to isolate mononuclear [M(HL)] complexes (M= Cu(II), Zn(II)). These precursors were then used to prepare M2Dy complexes. All Dy(III) ions are 6-coordinate & feature octahedral & trigonal antiprismatic geometries in Zn2Dy & Cu2Dy, respectively. The M2Dy complexes show slow relaxation of magnetization & retain solid-state structures in solution (confirmed by ESI-MS). The results show the “metalloligand” strategy can yield clusters with diverse magnetic properties.

References, if applicable:

1. Moore, D.A.; Fanwick, P.E.; Welch, M.J. Inorg. Chem. 1989, 28, 1504.
2. Nakai, H.; Seo, J.; Kitagawa, K.; Goto, T.; Matsumoto, T.; Ogo, S. Dalton Trans. 2016, 45, 9492.
3. Barta, C.A.; Bayly, S.R.; Read, P.W.; Patrick, B.O.; Thompson, R.C.; Orvig, C. Inorg. Chem. 2008, 47, 2294.

Hydroaminoalkylation with aliphatic amines enabled by the mecha-nistic investigation of cyclic N,O-chelating ureate tantalum catalysts

Pargol  Daneshmandkashani
@Pargol_D (https://twitter.com/pargol_d)
Post-doctoral Fellow at University of British Columbia, Vancouver, Canada

Pargol Daneshmand (UBC), Sorin Claudiu-Roşca (UBC), Rosalie Dalhoff (UBC), Kejun Yin (UBC), Rebecca C. DiPucchio (UBC), Ryan A. Ivanovich (uOttawa), Dilan E. Polat (uOttawa) , André M. Beauchemin (uOttawa), Laurel L. Schafer (UBC)

Abstract:

The first optimized N,O-chelated cyclic ureate tantalum catalyst can be used for the hydroaminoalkylation of 1-octene with challenging N-alkyl secondary amine substrates. This catalyst offers turnover frequencies of up to 60 h-1 and short reaction times of approximately 1 hour. Kinetic isotope effect (KIE) studies reveal that catalytic turnover is the limiting step. Mechanistic studies show that catalytic turnover is promoted by electron rich amine substrates (Hammett plot).

References, if applicable:

Towards the Preparation of Azide-Modified Silver Chalcogenolate Nanoclusters

Johanna Antonia de Jong
@JohdeJ (https://twitter.com/JohdeJ)
Undergraduate Student at University of Western Ontario, London, Canada

Abstract:

Ag nanoclusters (NCs) have applications in optical imaging, chemical sensing, and catalysis, but their ability to undergo interfacial surface chemistry is currently limited by the inertness of their organic ligands. Here we discuss progress towards functionalizing a Ag chalcogenolate NC with an azide capable of a biorthogonal click reaction: the Strain-Promoted Alkyne-Azide Cycloaddition. The ability to link molecules to the surface of NCs enables their properties to be tuned and enhanced.

References, if applicable:

Structure-Activity Relationships in Cationic and Neutral Indium Complexes for Ring-Opening Polymerization Reactions

Carlos  Diaz
@_cdlz_ (https://twitter.com/_cdlz_)
Graduate Student at University of British Columbia, Vancouver, Canada

Jane Fu, University of British Columbia, Canada. Parisa Mehrkhodavandi, University of British Columbia, Canada

Abstract:

Herein, we present different cationic indium with different side-arm donor groups and evaluate their effects on polymerization rates of cyclic ethers. Similarly, neutral complexes are evaluated for the ROP of cyclic esters and copolymerization of epoxides with carbon dioxide. Structure-function studies were conducted to better understand the different mechanisms involved and potentially improve the reactivity and control over the polymerizations

References, if applicable:

The Fe2(NO)2 Diamond Core: A Unique Structural Motif In Non-Heme Iron-NO Chemistry

Hai T Dong
@haidong1301 (https://twitter.com/haidong1301)
Graduate Student at University of Michigan, Ann Arbor, United States

Hai Dong, University of Michigan, Vietnam; Amy Speelman, University of Michigan, US; Claire Kozemchak, University of Michigan, US; Debangsu Sil, Pennsylvania State University, US; Carsten Krebs, Pennsylvania State University, US; Nicolai Lehnert, University of Michigan, US.

Abstract:

Many hs-{FeNO}8 complexes disproportionate by forming dinitrosyl iron complexes (DNICs). However, the mechanism of this reaction is not understood. The hs-{FeNO}7 complex, [Fe(TPA)(NO)(OTf)](OTf) (1) was synthesized and characterized by different spectroscopic methods and X-ray crystallography. Upon reduction of 1 with 1 eq. of CoCp2 we isolated and structurally characterized a novel dimer, [Fe2(TPA)2(NO)2](OTf)2, which we propose to be a potential intermediate of DNIC formation.

References, if applicable:

Dong, H. T.; Speelman, A. L.; Kozemchak, C. E.; Sil, D.; Krebs, C.; Lehnert, N. Angew. Chem. Int. Ed. 2019, 58, 17695-17699.

Synthesis and Structures of Anionic Rhenium Polyhydride Complexes of Boron-Hydride Ligands and their Application in Catalysis

Liam J Donnelly
@LiamDonChem (https://twitter.com/LiamDonChem)
Graduate Student at The University of Edinburgh, Edinburgh, United Kingdom

Simon Parsons; Carole Morrison; Stephen Thomas; Jason Love, Edinburgh University, United Kingdom

Abstract:

The rhenium complex, [K(DME)(18-c-6][ReH7(Bpin)3] comprising hydride and boron ligands only, has been synthesized by exhaustive deoxygenation of the perrhenate anion (ReO4−) with pinacol borane (HBpin). The structure of this complex was analysed by X-ray crystallography, NMR spectroscopy, and DFT calculations. This complex is a catalyst for the hydroboration of pyridines under simple operating procedures and is also a reagent for the C-H borylation of toluene.

References, if applicable:

Donnelly, L. J.; Parsons, S.; Morrison, C. A.; Thomas, S. P.; Love, J. B. Submitted

Activation of a Mn(II)Mn(III)-Peroxide with Relevance to the Catalytic Cycle of Class Ib RNRs

Lorna M Doyle
@ChemLorna (https://twitter.com/ChemLorna)
Graduate Student at Trinity College Dublin, Dublin, Ireland

Shuangning Xu, University of Minnesota, USA, Lawrence Que Jr.,  University of Minnesota, USA, Aidan R. McDonald, Trinity College Dublin, Ireland

Abstract:

Ribonucleotide reductase enzymes (RNR) convert ribonucleotides to deoxyribonucleotides.[1] The biomimetic complex, [Mn(II)2(BPMP)(OAc)2](ClO4) (1) reacts with superoxide, the RNR oxidising agent, to form an Mn(II)Mn(III)-peroxide which reacts with acids to form an Mn(III)Mn(IV) species. mimicking the cycle of RNR and suggests the role acid activation in the cycle of RNRs.[2],[3]

References, if applicable:

[1]          Cotruvo, J. A.; Stubbe, J. Annu. Rev. Biochem. 2011, 80 (1), 733.

[2]          Cotruvo, J. A.; Stich, T. A.; Britt, R. D.; Stubbe, J. J. Am. Chem. Soc. 2013, 135 (10), 4027.

[3]                         (a) Suzuki, M.; Mikuriya, M.; Murata, S.; Uehara, A.; Oshio, H.; Kida, S.; Saito, K. Bull. Chem. Soc. Jpn. 1987, 60 (12), 4305 (b) Blanchard, S.; Blondin, G.; Rivière, E.; Nierlich, M.; Girerd, J.-J. Inorg.Chem. 2007, 42 (15), 4568.

All-solution-processed organic light-emitting diodes based on a novel and versatile benzothiazole-salophen derivative

Luis Gustavo Duarte
@lgalvesduarte (https://twitter.com/lgalvesduarte)
Post-doctoral Fellow at University of Campinas, Campinas, Brazil

José Germino, University of Campinas, Brazil; Cristina Barboza,  Jônatas Berbigier, Universidade Federal do Rio Grande do Sul, Brazil; Cristina Barboza, Polish Academy of Sciences; Rodrigo Mendes, Uniersity of São Paulo, Brazil; Marcelo Faleiros, University of Campinas, Brazil; Fabiano Rodembusch, Universidade Federal do Rio Grande do Sul, Brazil; Teresa Atvars, University of Campinas, Brazil

Abstract:

The N,N’-bis(salicylidene)-(2-(3’,4’-diaminophenyl)benzothiazole (BTS), that undergoes Excited State Intramolecular Proton Transfer process (ESIPT) was synthesized and characterized as a strategy to construct fluorescence emission covering the entire visible spectrum. BTS was studied by steady-state and time-resolved spectroscopies. Its ESIPT balance and Zn coordination compound allowed the production of all-solution processed WOLEDs in host-guest composites.

References, if applicable:

Octaboraneyl Complexes of Nickel: Monomers for Redox-Active Coordination Polymers

Maeve C Dufour
@maevedufour_11 (https://twitter.com/maevedufour_11)
Undergraduate Student at University of Windsor, Windsor, Canada

Abstract:

We establish the preparation, characterization, and reactivity of 1,2-bis(di(3-dicyclohexylboraneyl)propylphosphino)-C₂H₆(P2BCy4). The coordination of P2BCy4 with nickel, results in Ni(P2BCy4)2 and is reactive with Lewis bases. Addition of 4,4′-bipyridine, creates an air-sensitive coordination polymer.Characterized by solid-state NMR and EPR, a charge transfer polymer was identified from an intramolecular Ni → 4,4′-bpy ET, providing oxidized nickel sites and reduced 4,4′-bpy radical anion sites.

References, if applicable:

Drover, M. W.; Dufour, M.C.; Lesperance-Nantau, L.A.; Noriega, R.P.; Levin, K.; Schurko, R.W. Chem. –Eur. J. 2020, DOI: 10.1002/chem.202001218

Efficient Catalytic Hydrogenolysis of Halosilanes to Hydrosilanes Using an Iridium Pincer Complex and Superbases

Gabriel  Durin
@DurinGabriel (https://twitter.com/DurinGabriel)
Graduate Student at French Alternative Energies and Atomic Energy Commission, Paris, France

Gabriel Durin, Jean-Claude Berthet, Emmanuel Nicolas, Thibault Cantat, French Alternative Energies and Atomic Energy Commission, France

Abstract:

Hydrosilanes are convenient reductants but are produced via energy intensive processes3 and generate, after use, silicon oxides wastes such as siloxanes, which are difficult to recycle. These limitations call for the development of catalytic processes able to transform Si‒O bonds in siloxanes into Si‒H hydrides. Previous reports4 have shown that chlorosilanes can be prepared from siloxanes. We report here an efficient hydrogenolysis of chlorosilanes (up to 79 %) using [(tBuPOCOP)IrHCl] complex.

References, if applicable:

1. Monsigny, L.; Feghali, E.; Berthet, J. C.; Cantat, T. Green Chem., 2018, 20, 1981.
2. Riduan, S. N.; Zhang, Y.; Ying, J. Y. Angew. Chem. Int. Ed., 2009, 48, 3322.
3. Kalchauer, W.; Pachaly, B. In Handbook of Heterogeneous Catalysis.Wiley, 2008, 2635-2647.
4. (a) Di Giorgio, P. A.; Strong, W. A.; Sommer, L. H.; Whitmore, F. C. J. Am. Chem. Soc., 1946, 68, 1380 (b) Bailey, D. L.; Sommer, L. H.; Whitmore, F. C. J. Am. Chem. Soc., 1948, 70, 435-436 (c) Masaoka, S.; Bannoa, T.; Ishikawa, M. J. Organomet. Chem., 2006, 691, 174–181 (d) Roberts, J. M.; Eldred, D. V.; Katsoulis, D. E. Ind. Eng. Chem. Res., 2016, 55, 1813-1818.
5. (a) Tsushima, D.; Igarashi, M.; Sato, K.; Shimada, S. Chem. Lett., 2017, 46, 1532–1534.

See also hydrogenolysis of chlorosilanes in the presence of additives (NaI, NaBAr4F) : (b) Beppu, T.; Sakamoto, K.; Nakajima, Y.; Matsumoto, K.; Sato, K.; Shimada, S. J. Org. Chem., 2018, 869, 75-80. (c) Glüer, A.; Schweizer, J. I.; Karaca, U. S.; Würtele, C.; Diefenbach, M.; Holthausen, M. C.; Schneider, S. Inorg. Chem., 2018, 57, 13822-13828.

A Direct Comparison of Thiolate vs. Amido Donors for Bifunctional Catalysis with Mn and Cu Catalysts

Matthew R Elsby
@matthew_elsby (https://twitter.com/matthew_elsby)
Graduate Student at University of Ottawa, Ottawa, Canada

1. Tom Baker

Abstract:

Base-metal complexes that utilize metal-ligand-cooperativity are highly sought.  Two new Cu-SNS complexes were synthesized to compare the activity of an amido vs a thiolate donor in outer-sphere carbonyl reactivity Mechanistic studies involving a “forced” outer-sphere mechanism led to the design of Mn catalysts. Insight into the Mn oxidation state in the active species in outer-sphere carbonyl reductions employing Mn(II) precatalysts are discussed.

References, if applicable:

10402. Higashi, S. Kusumoto, and K. Nozaki, Cleavage of Si–H, B–H, and C–H Bonds by Metal-Ligand Cooperation, Chem. Rev, 2019, 119, 10393-10402. DOI: 10.1021/acs.chemrev.9b00262

Fusing Isothiocyanates and Perfluorinated Boranes

Malte  Fischer
@FiMalte (https://mobile.twitter.com/FiMalte)
Post-doctoral Fellow at Leibniz-Institut für Katalyse (Rostock, Germany), , Germany

Marc Schmidmann, Carl von Ossietzky Universität Oldenburg, Germany

Abstract:

A3

References, if applicable:

Solvent-free mechanochemical synthesis of ultrasmall nickel phosphide nanoparticles and their use as catalysts for the hydrogen evolution reaction

Blaine G Fiss
@Canuk_Chemist (https://twitter.com/Canuk_Chemist)
Graduate Student at McGill University, Montreal, Canada

Nhu Nang Vu, Laval University, Canada. Georgia Douglas, McGill University, Canada. Trong-On Do, Laval University, Canada. Tomislav Friščić, McGill University, Canada. Audrey Moores, McGill University, Canada

Abstract:

We demonstrate the mechanochemical application of sodium phosphide as an excellent solid-state phosphorus source for the synthesis of Ni2P nanoparticles below 3 nm in diameter, the smallest seen for the mechanochemical synthesis of metal phosphides. These nanoparticles, supported on g-C3N4, were successful for the hydrogen evolution reaction, generating 233.9 μmol g-1 h-1 of hydrogen, over 3 hours using broad spectrum light at room temperature, as well as being readily recyclable and reusable.

References, if applicable:

Shi, Y.; Zhang, B. Chem. Soc. Rev. 2016, 45, 1529.

Fiss, B. G.; Vu, N. N.; Douglas, G.; Do, T. O.; Friščić, T.; Moores, A. Submitted. 2020.

Vanadium Aminopyridinate Catalysts for the Reductive Coupling of Alcohols

Amanda A Fogh
@mandyfogh (https://twitter.com/mandyfogh)
Undergraduate Student at University of British Columbia, Vancouver, Canada

Samual Griffin, Graduate Student, Canada

Abstract:

The reductive coupling of alcohols is beneficial for the re-functionalization of biomass-derived material. Vanadium catalysts were investigated for this transformation. A vanadium aminopyridinate catalyst was able to perform the reductive coupling of alcohols more efficiently than previously reported catalytic systems. Many vanadium aminopyridinate complexes were synthesized towards mechanistic understanding of this catalytic system and provided insight into this underdeveloped field of study.

References, if applicable:

Metal Complexes as a Promising Source for New Antimicrobials?

Angelo  Frei
@Angelo_Frei (https://twitter.com/angelo_frei)
Post-doctoral Fellow at The University of Queensland, Brisbane, Australia

Angelo Frei, The University of Queensland, Australia; Johannes Zuegg, The University of Queensland, Australia; Mark Blaskovich, The University of Queensland, Australia.

Abstract:

Metal complexes are a cornerstone of medicinal chemistry, with compounds such as the anticancer drug Cisplatin still constituting one of the most important chemotherapeutics in the clinics today. However, metals have remained largely unexplored for antimicrobial applications. We have tested the antimicrobial activity of over 300’000 crowd-sourced compounds and found that metal complexes have a significantly higher hit-rate against bacteria and fungi than purely organic molecules.

References, if applicable:

Frei, A.;  Zuegg, J.;  Elliott, A. G.;  Baker, M.;  Braese, S.;  Brown, C.;  Chen, F.;  G. Dowson, C.;  Dujardin, G.;  Jung, N.;  King, A. P.;  Mansour, A. M.;  Massi, M.;  Moat, J.;  Mohamed, H. A.;  Renfrew, A. K.;  Rutledge, P. J.;  Sadler, P. J.;  Todd, M. H.;  Willans, C. E.;  Wilson, J. J.;  Cooper, M. A.; Blaskovich, M. A. T., Metal complexes as a promising source for new antibiotics. Chem. Sci. 2020, 11, 2627.

Ti-Mediated Intermolecular Diamination of Alkynes via [4+2]-Cycloaddition Reactions with Trapped [2+2] Intermediates

Connor Wesley Frye
@ConnorFrye42 (https://twitter.com/ConnorFrye42)
Graduate Student at University of Minnesota, Minneapolis, United States

Dominic Egger, Errikos Kounalis, Adam J. Pearce, Ian Tonks

Abstract:

Accessing unsymmetrical α-diimines through acid-catalyzed condensations can be synthetically challenging. Here we report the intermolecular diamination of alkynes to afford α-diimines from Ti imidos, alkynes, nitriles, and C-nitrosos. This proposed to occur by the [4+2]-cycloaddition of a nitroso to the Ti and γ-carbon of a trapped [2+2] diazatitanacyclohexadiene intermediate, followed by two subsequent cycloreversion steps to eliminate nitrile and afford the α-diimine and a Ti oxo.

References, if applicable:

Triptycenyl phosphines as platform for the design of frustrated Lewis pair

Mathieu  Gama
@GamaMathieu (https://twitter.com/GamaMathieu)
Graduate Student at University of Namur, Namur, Belgium

Lei Hu, University of Louvain, Belgium. Raphaël Robiette, University of Louvain, Belgium. Guillaume Berionni, University of Namur, Belgium

Abstract:

In 2008, Stephan defined FLPs as sterically hindered Lewis acids and bases that cannot form a covalent Lewis adduct because of steric repulsions. [1]

In this work, the synthesis of triptycene-derived sterically hindered phosphines and their associations with reference Lewis acids systems of calibrated electrophilicities and Lewis acidities are investigated in the context of the development of new frustrated Lewis pairs.

References, if applicable:

1. D. W. Stephan, ““Frustrated Lewis pairs”: a concept for new reactivity and catalysis”, Org. Biomol. Chem. 2008, 6, 1535

Efficient Transfer Hydrogenation of Ketones using Methanol as Liquid Hydrogen Organic Carrier

NIDHI  GARG
@Nidhigarg1994 (https://twitter.com/Nidhigarg1994)
Graduate Student at Ph.D.- IIT Kanpur, DELHI, INDIA

Nidhi Garg, Soumen Paira, Basker Sundararaju*, Associate professor, IIT Kanpur, India. basker@iitk.ac.in

Abstract:

Instead of conventional, stoichiometric reducing agents or hazardous H2 gas with transition metals, transfer hydrogenation of ketones with LOHC using transition metals is a viable alternative.But so far, only a few reports are there where methanol act as hydrogen source. We herein present, an efficient transfer hydrogenation of ketones by homogeneous Iridium-Bipyridonate system using methanol as LOHC. The methodology is efficient, practical, chemoselective with a wide array of ketones as scope.

References, if applicable:

Nielsen, M.; Alberico, E.; Baumann, W.; Drexler, H.-J.; Junge, H.; Gladiali, S.; Beller, M. Nature 2013, 495, 85.

Fujita, K.-I.; Kawahara, R.; Aikawa, T.; Yamaguchi, R. Angew. Chem. Int. Ed. 2015, 54, 9057.

Campos, J.; Sharninghausen, L. S.; Manas, M. G.; Crabtree, R. H. Inorg. Chem. 2015, 54, 5079.

Unlocking the catalytic potential of  tris(3,4,5-trifluorophenyl)borane using microwave irradiation

Lukas J Gierlichs
@LGierlichs (https://twitter.com/LGierlichs)
Graduate Student at Cardiff University, Cardiff, United Kingdom

Jamie Carden, Cardiff University, UK, Duncan Wass, Bristol University/Cardiff University, UK, Duncan Browne, Cardiff University/UCL, UK, Rebecaa Melen, Cardiff University, UK

Abstract:

Enabling technology is rarely employed in main group catalysis. In this work microwave irradiation was used to enhance the reactivity of tris(3,4,5-trifluorophenyl)borane in the hydroboration of unsaturated substrates.

References, if applicable:

1. J. R. Lawson and R. L. Melen, Inorg. Chem., 2017, 56, 8627-8643.
2. J. L Carden, A. Dasgupta, and R. L. Melen, Chem. Soc. Rev., 2020, 49, 1706-1725.
3. Q. Yin, Y. Soltani, R. L. Melen and M. Oestreich, Organometallics, 2017, 36, 2381-2384.
4. C. O. Kappe, Angew. Chem. Int. Ed., 2004, 43, 6250-6284.
5. J. L Carden, L. J. Gierlichs, D. F. Wass, D. L. Browne, and R. L. Melen, Chem. Comm., 2019, 55, 318-321.

The Metalation of Neuronal Peptides with Cu(II)/(I) Modulates the Formation of Reactive Oxygen Species

Camilla  Golec
@camillagolec (https://twitter.com/camillagolec)
Undergraduate Student at Trent University, Peterborough, Canada

Saba Anwar, Oakland University, United States – Sanela Martic, Trent University, Canada

Abstract:

Tau protein aggregation has been linked to the pathogenesis of Alzheimer’s disease (AD). However, the relationship between metal ions and the protein has not been characterized. Biologically relevant metal ions contribute to normal cellular function, but dyshomeostasis and the formation of reactive oxygen species (ROS) can lead to diseases (1-2).  Several spectroscopic methods were used to study the role of Cu(II)/(I) on the formation of ROS in the presence of brain-related tau peptides.

References, if applicable:

1. Faller, P.; Hureau, C. Chem. Eur. J. 2012, 18, 15910.
2. Jiang, D.; Li, X.; Liu, L,; Yagnik, G.; Zhou, F.; Tabner, J.; Allsop, D. J. Bio. Chem. 2014, 289, 12052.

Rational Design Approach for Improved Thermomechanical Properties in DPP-based Polymers

Renée B Goodman
@ReneeBGoodman (https://twitter.com/ReneeBGoodman)
Undergraduate Student at Universoty of Windsor, Windsor, Canada

Michael U. Ocheje, University of Windsor, Canada; Song Zhang, University of Southern Mississippi, United States; Dr. Xiaodan Gu, University of Southern Mississippi, United States; Dr. Simon Rondeau-Gagné, University of Windsor, Canada

Abstract:

Understanding the fundamental structure-mechanical property relationship for semiconducting polymers is essential for designing more flexible organic electronics and to develop rational tools for the preparation of soft conjugated polymers. Through backbone engineering, our team is investigating the effect of fused and isolated thiophene moieties incorporated to diketopyrrolopyrrole-based conjugated polymers, and the effect of side chains on the thermomechanical properties of the semiconductors.

References, if applicable:

1. S. Zhang, M. U. Ocheje, S. Luo, D. Ehlenberg, B. Appleby, D. Weller, D. Zhou, S. Rondeau-Gagné and X. Gu, Macromol. Rapid Commun., 2018, 39, 1–8
2. S. Zhang, M. U. Ocheje, L. Huang, L. Galuska, Z. Cao, S. Luo, Y. H. Cheng, D. Ehlenberg, R. B. Goodman, D. Zhou, Y. Liu, Y. C. Chiu, J. D. Azoulay, S. Rondeau-Gagné and X. Gu, Adv. Electron. Mater., 2019, 5, 1–11.

Introducing Hemilability to Cationic Indium Complexes

Chatura  Goonesinghe
@chaturad_g (https://twitter.com/chaturad_g)
Graduate Student at University of British Columbia, Vancouver, Canada

Hootan Roshandel, UBC, Canada. Carlos Diaz, UBC, Canada. Hyuk-Joon Jung, UBC, Canada. Kudzanai Nyamayaro, UBC, Canada. Maria Ezhova, UBC, Canada. Parisa Mehrkhodavandi, UBC, Canada

Abstract:

Hemilabile ligands can influence the behavior of organometallic complexes. We report a series of cationic indium complexes bearing ligands with hemilabile pendant arms. Stability and temperature behavior of these complexes are correlated to the donicity pendant groups. The presence external donors result in fluxional behavior of the hemilabile arm with de-coordination in the presence of strong donors. This behavior allows these ligands to be used for tuning reactivity cationic indium species.

References, if applicable:

(1) Goonesinghe, C.; Roshandel, H.; Diaz, C.; Jung, H.-J.; Nyamayaro, K.; Ezhova, M.; Mehrkhodavandi, P. Cationic Indium Catalysts for Ring Opening Polymerization: Tuning Reactivity with Hemilabile Ligands. Chem. Sci. 2020, 11 (25), 6485–6491.

(2) Diaz, C.; Ebrahimi, T.; Mehrkhodavandi, P. Cationic Indium Complexes for the Copolymerization of Functionalized Epoxides with Cyclic Ethers and Lactide. Chem. Commun. 2019, 55 (23), 3347–3350.

(3) Jung, H.-J.; Chang, C.; Yu, I.; Aluthge, D. C.; Ebrahimi, T.; Mehrkhodavandi, P. Coupling of Epoxides and Lactones by Cationic Indium Catalysts To Form Functionalized Spiro-Orthoesters. ChemCatChem 2018, 10 (15), 3219–3222.

High-Efficiency Blue Photoluminescence in the Cs2NaInCl6:Sb3+ Double Perovskite Phosphor

Matt  Gray
@Gray3311 (https://twitter.com/Gray3311)
Graduate Student at The Ohio State University, Columbus, United States

Shruti Hariyani, University of Houston, USA T. Amanda Strom, UCSB, USA Jackson Majher, The Ohio State University, USA, Jakoah Brgoch, University of Houston, USA Patrick Woodward, The Ohio State University, USA

Abstract:

The luminescent properties of a lead-free double perovskite Cs2NaInCl6 doped with Sb3+ are explored. The host crystal structure is a cubic double perovskite and has rock salt ordering of Na+ and In3+ ions. It is a wide bandgap compound (Eg ≈ 5.4 eV), and substitution with Sb3+ leads to strong absorption in the UV due to localized 5s2 → 5s15p1 transitions on Sb3+ centers. Radiative relaxation via a 3P1 → 1S0 transition, leads to intense blue luminescence, centered at 445 nm, with a PLQY of 79%.

References, if applicable:

Gray, M. B.; Hariyani, S.; Strom, T. A.; Majher, J. D.; Brgoch, J.; Woodward, P. M. High-efficiency blue photoluminescence in the Cs2NaInCl6:Sb3+ double perovskite phosphor. J. Mater. Chem. C., 2020, 8, 6797-6803

Elucidating the Mechanism of Oxidative Addition of Alkyl Substrates to [Ni(COD)(dppf)].

Megan  Greaves
@megangreaves7 (https://twitter.com/MeganGreaves7)
Graduate Student at University of Strathclyde, Glasgow, UK

David Nelson, University of Strathclyde, UK. Guy Lloyd-Jones, University of Edinburgh, UK. Thomas Ronson, AstraZeneca, UK.

Abstract:

This work examines the kinetics of this reaction with alkyl substrates, and shows that Ni(dppf)2 is the active nickel species in the reaction with alkyl halides.(1) These reactions are first order in Ni(COD)(dppf), dppf, and alkyl halide, and inverse first order in COD. The rate expression is consistent with a rapid formation of Ni(dppf)2 and a subsequent irreversible reaction with alkyl halide. The experimental data is supported by DFT studies which suggest a halide abstraction mechanism.

References, if applicable:

Bajo, S.; Laidlaw, G.; Kennedy, A., R.; Sproules, S.; Nelson, D., J. Organometallics, 2017, 36, 1662

It’s Better with Salt: Aqueous Ring-Opening Metathesis Polymerization at Neutral pH

Marcus C Grocott
@marcus_grocott (https://twitter.com/marcus_grocott)
Undergraduate Student at University of Birmingham, Birmingham, UK

Abstract:

At present, acidic media is required to avert catalyst decomposition during Aqueous Ring-Opening Metathesis Polymerization, limiting its scope to non-pH-sensitive substrates. However, it is found that catalyst activity and lifetime can be improved by chloride salts at neutral pH. The ability to conduct aqueous metathesis at neutral pH is expected to enable new research avenues for polymer and organic synthesis by expanding the synthetic toolbox for reactions that involve pH-sensitive substrates.

References, if applicable:

Exploring Magnetic XY Behavior in a Quasi-2D Anisotropic Triangular Lattice of Cu(II) by Functionalized Graphene

Kriti  Gupta
@2342Kriti (https://twitter.com/2342Kriti)
Graduate Student at Indian Institute of Science Education and Research (IISER), , India

Kriti Gupta, Department of Chemistry, Indian Institute of Science Education and Research, Pune 411008, India; Arun Dadwal, Physical and Materials Chemistry Division, National Chemical Laboratory, Pune 411008, India; Plawan Kumar Jha, Department of Chemistry, Indian Institute of Science Education and Research, Pune 411008, India; Anil Jain, Solid State Physics Division, Bhabha Atomic Research Centre, Mumbai 400085, India, Homi Bhabha National Institute, Anushakti Nagar, Mumbai 400094, India; S. M. Yusuf, Solid State Physics Division, Bhabha Atomic Research Centre, Mumbai 400085, India, Homi Bhabha National Institute, Anushakti Nagar, Mumbai 400094, India; Pattayil A. Joy, Physical and Materials Chemistry Division, National Chemical Laboratory, Pune 411008, India; Nirmalya Ballav, Department of Chemistry, Indian Institute of Science Education and Research, Pune 411008, India

Abstract:

Botallackite (Bo) (Cu2(OH)3Br), an anisotropic triangular spin lattice is stabilized over 2D reduced graphene oxide (rGO) via simple oxidation reduction reaction. Such an anchoring led to the oriented growth of Bo crystallites in Bo-rGO system. Bo-rGO was found to be magnetically active with a Néel transition at ∼8.9 K, crossing over to possible XY anisotropy at ∼5 K as revealed by dc and ac susceptibility measurements –an unprecedented observation in the field assigned to an interfacial effect.

References, if applicable:

Gupta, K.; Dadwal, A.; Jha, P. K.; Jain, A.; Yusuf, S. M.; Joy, P. A.; Ballav, N. Inorg. Chem. 2020, 59, 6214.

Selective C-F bond Functionalization of Polyfluorocarbon Using Frustrated Lewis Pair Approach

Richa  Gupta
gupta_richa1434 (https://twitter.com/gupta_richa1434)
Graduate Student at National University of Singapore, Singapore, Singapore

Dipendu Mandal, National University of Singapore, Singapore. Amit Kumar Jaiswal, National University of Singapore, Singapore. Rowan Young, National University of Singapore, Singapore.

Abstract:

We have developed a catalytic frustrated Lewis pair approach for selective C-F bond activation in polyfluoromethyl groups with phosphine bases. The resulting phosphonium salts can be functionalized via Wittig coupling, photoredox alkylation, nucleophilic transfer and hydrophosphination reactions to install diverse functional groups into the activated C-F position. This reaction allows simple access to fluoro compounds of current interest to pharmaceutical, agrochemistry, and materials sciences.

References, if applicable:

10682. Gupta, D. Mandal, R. D. Young, J. Am. Chem. Soc., 2018, 140, 10682.
10683. Gupta, D. Mandal, A. K. Jaiswal, R. D. Young, J. Am. Chem. Soc. 2020, 142, 2572.

Hydrosilylative Reduction of Tertiary Amides to Amines Catalyzed by N-(Phosphinoaryl)anilido Complexes of Iron and Cobalt

Dylan J Hale
@DylanHale1995 (https://twitter.com/DylanHale1995)
Graduate Student at Dalhousie University, Halifax, Canada

Luke J. Murphy, Dalhousie University, Canada Laura Turculet, Dalhousie University, Canada

Abstract:

The synthesis and characterization of low-coordinate Fe(II) and Co(II) complexes supported by the monoanionic P,N-ligand N-(2-dicyclohexylphosphinophenyl)-2,6-diisopropylanilide are described. Three-coordinate (P,N)Fe-hexamethyldisilazide complex (2), and four-coordinate (P,N)Fe- (3-Fe) and (P,N)Co-alkyl (3-Co) complexes were evaluated as pre-catalysts for the hydrosilylative reduction of amides with PhSiH3 (5 mol% pre-catalyst, 1 equiv. PhSiH3, 80°C, 1–24 h).

References, if applicable:

The Synthesis of Boron-Nitrogen Doped Indenofluorenes for Organic Electronic Applications

Tyler J Hannah
@THannah77 (https://twitter.com/THannah77)
Undergraduate Student at University of Calgary, Calgary, Canada

Evan Patrick, University of Calgary, Canada; Gregory Welch, University of Calgary, Canada; Warren Piers, University of Calgary, Canada.

Abstract:

This project is concerned with the synthesis of a boron-nitrogen doped indenofluorene for use as a non-fullerene acceptor in organic solar cell (OSC) applications. Previous work on this indenofluorene core was able to generate a power conversion efficiency of 2 % in an OSC device when used as an acceptor. Synthetic efforts focused on improving the device efficiency utilizing this B-N core. A synthetic pathway to the target was not able to be established, however a key intermediate was obtained.

References, if applicable:

1. Morgan, M. M.; Nazari, M.; Pickl, T.; Rautiainen, J. M.; Tuononen, H. M.; Piers, W.; Welch, G. C.; Gelfand, B. S. Chem. Commun. 2019, 55, 11095-11098.

Synthesis and Coordination Properties of Antimony Based Pincer Ligands

Alexander  Harrison
@AIex_Harrison (https://twitter.com/aiex_harrison/)
Graduate Student at University of Calgary, Calgary, Canada

Chris Gendy, Meagan Boehr

Abstract:

PCP-pincer complexes are among the most prominent representatives of their class. Comparatively, the chemistry of their heavier analogs has seen little development. Although the coordination chemistry of stibine ligands is well developed, no pincer complexes with antimony pendant donors have been reported.1 Our investigation into these ligand platforms has yielded both surprising and expected reactivity with Rh and Ir. The synthesis and reactivity of this SbOCOSb pincer ligand will be presented.

References, if applicable:

1. Morales-Morales, D. Mini. Rev. Org. Chem. 2008, 5, 141–152.

Characterization of Copper Hyponitrite Complexes using X-ray Absorption Spectroscopy

Brenda  Henriquez
@Brenda_H_2020 (https://twitter.com/Brenda_H_2020)
Graduate Student at California State Polytechnic University, Pomona, Pomona, United States

Timothy Warren, Georgetown University, USA; Subrata Kundu, Georgetown University, USA; Pokhraj Gosh, Georgetown University, USA

Abstract:

Discrete diketiminate copper complexes formed in solution were analyzed by X-ray absorption spectroscopy. The X-ray absorption near edge structure analysis determined the oxidation state of compound 1, 2, and 4 to be +1, while compound 3 has an oxidation state of +2. The extended X-ray absorption determines coordination environment and determined compound 4 is consistent with a hyponitrite bound, suggesting one of the first examples hyponitrite complex was synthesized and isolated.

References, if applicable:

Germanium Catechol Complexes: Synthesis and Assessment of their Lewis Acidity and Catalytic Activity

Andrew T Henry
@AndrewHenryChem (https://twitter.com/andrewhenrychem)
Graduate Student at University of Western Ontario, London, Canada

Abstract:

Main group catalysts are currently being explored as promising alternatives to transition metal-based catalysts. While there are multiple examples of silicon Lewis acids,[1,2] germanium Lewis acid catalysts remain scarce. The synthesis of bis(catecholato)germanium complexes with two nitrogen donors has recently been reported.[3] The synthesis of a variety of germanium catechol complexes, as well as an assessment of the Lewis acidity and catalytic activity will be presented.

References, if applicable:

1. Maskey, R.; Schädler, M.; Legler, C.; Greb, L.; Angew. Chem. Int. Ed. 2018, 57, 1717.
2. Libermann-Martin, A. L.; Bergman, R. G.; Tilley, T. D.; J. Am. Chem. Soc. 2015, 137, 5328.
3. Glavinović, M.; Krause, M.; Yang, L.; McLeod, J. A.; Liu, L.; Baines, K. M.; Friščić, T.; Lumb, J. P.; Sci. Adv. 2017, 3, e1700149.

CuO nanoparticles/Ti3C2Tx MXene hybrid Nanocomposites for Detection of Toluene Gas

Angga  Hermawan
@anggahermaw (https://twitter.com/anggahermaw)
Graduate Student at Institute of Multidisciplinary Research for Advanced Materials (IMRAM), Tohoku University, Sendai, Japan

Angga HERMAWAN, Biao ZHANG, Ardiansyah TAUFIK, Yusuke ASAKURA, Takuya HASEGAWA, Jianfeng ZHU, Pei SHI, Shu YIN

Abstract:

We report a facile preparation of CuO/ Ti3C2Tx MXene hybrids via electrostatic self-assembly. The CuO/Ti3C2Tx MXene exhibited the improved toluene gas sensing response (Rg/Ra) of 11.4, which is nearly 5 times higher than that of the pristine CuO nanoparticles (2.3) to 50 ppm of toluene at 250 oC. Such excellent performance showed the promising applications of metal oxides/2D hybrid materials for VOCs gas sensing.

References, if applicable:

Hermawan, A.; Zhang, B.; Taufik, A.; Asakura, Y.; Hasegawa, T.; Zhu, J.;, Shi, P.; Yin, S. ACS Appl. Nano Mater. 2020, 3 (5),  4755–4766.

Di-tert-butyldiphosphatetrahedrane: Catalytic Synthesis and Reactivity of the Elusive Phosphaalkyne Dimer

Gabriele  Hierlmeier
@GHierlmeier (https://twitter.com/ghierlmeier)
Graduate Student at University of Regensburg, Regensburg, Germany

Peter Coburger, Michael Bodensteiner, Robert Wolf

Abstract:

While tetrahedranes as a family are scarce, neutral heteroatomic species are all but unknown, with the only reported example being AsP3.[1]

We present the isolation of di-tert-butyldiphosphatetrahedrane, (tBuCP)2, a neutral heteroatomic molecular tetrahedron which also is the long-sought-after free phosphaalkyne dimer.[2] (tBuCP)2 is formed from the monomer tBuCP in a nickel-catalyzed dimerization reaction using [(NHC)Ni(CO)3] (NHC = IMes, IPr).[3]

References, if applicable:

[1] B. M. Cossairt, M.-C. Diawara, C. C. Cummins, Science 2009, 323, 602.

[2] A. Chirila, R. Wolf, J. C. Slootweg, K. Lammertsma, Coord. Chem. Rev. 2014, 270–271, 57.

[3] G. Hierlmeier, P. Coburger, M. Bodensteiner, R. Wolf, Angew. Chem. Int. Ed. 2019, 58, 16918; Angew. Chem. 2019, 131, 17074.

Iron Complexes with N-Heterocyclic Bidentate Carbene Ligands

Alexis S Hoxie
@alexis_chem (https://twitter.com/alexis_chem)
Undergraduate Student at California State Polytechnic University, Pomona, , USA

Dr. S. Chantal E. Stieber, California State Polytechnic University, Pomona, USA

Abstract:

Iron complexes with bidentate N-Heterocyclic carbene ligands (RNHC2; R = alkyl or aryl) have not been widely reported and have potential to be catalysts for ranges of chemical transformations. This work aims to make new Fe0 pre-catalysts with MesNHC2 ligands. MesNHC2 was synthesized from mesitylimidazole, followed by addition of CH2Br2 to form a bis(imidazolium) salt. The salt was deprotonated with KHMDS and reacted with FeCl2 to synthesize the corresponding FeCl2 complex, (MesNHC2Me)FeCl2.

References, if applicable:

Tethered tungsten-alkylidenes for the synthesis of cyclic polynorbornene via REMP: Unprecedented stereoselectivity and trapping of key intermediates

Vineet K Jakhar
@jakhar_vineet (https://twitter.com/jakhar_vineet)
Graduate Student at University of Florida, Gainesville, United States

Digvijayee Pal, University of Florida, Department of Chemistry, USA;  Ion Ghiviriga, University of Florida, Department of Chemistry, USA; Khalil A. Abboud, University of Florida, Department of Chemistry, USA; Brent S. Sumerlin, University of Florida, Department of Chemistry, USA; Adam S. Veige, University of Florida, Department of Chemistry, USA.

Abstract:

This report describes an approach for preparing tethered tungsten-imido alkylidene complexes featuring a tetraanionic pincer ligand. Treating the tungsten alkylidyne [tBuOCO]W≡C(tBu)(THF)2 with isocyanates leads to cycloaddition occurring exclusively at the C=N bond to generate the tethered tungsten-imido alkylidenes. Unanticipated intermediates reveal themselves, including the discovery of [(O2CtBuC=)W(η2-(N,C)-RNCO)(THF)] and an unprecedented decarbonylation product [(tBuOCO)W(≡NR)(tBuCCO)].

References, if applicable:

Jakhar, V.; Pal, D.; Ghiviriga, I.; Abboud, K. A.; Sumerlin, B. S.; Veige, A. S.

Indium-catalyzed block copolymerization of lactide and methyl methacrylate by sequential addition

Hyuk-Joon  Jung
@Chem_Joon (https://twitter.com/Chem_Joon)
Graduate Student at University of British Columbia, Vancouver, Canada

Parisa Mehrkhodavandi, University of British Columbia, Canada; Insun Yu, University of British Columbia, Canada; Kudzanai Nyamayaro, University of British Columbia, Canada

Abstract:

We synthesized a series of neutral and cationic indium

complexes supported by tridentate Schiff base ligands and investigated

their reactivities for the homo- and block copolymerization of lactide or ε-

caprolactone and methyl methacrylate by sequential addition. The block copolymers

were stringently characterized by size exclusion chromatography (SEC),

diffusion ordered NMR spectroscopy (DOSY), differential scanning

calorimetry (DSC), and fractional precipitation techniques.

References, if applicable:

Jung, H.-J.; Yu, I.; Nyamayaro, K.; Mehrkhodavandi, P. ACS Catal. 2020, 10, 6488-6496.

A multistimuli responsive heteroleptic iridium( III ) complex: role of hydrogen bonding in probing solvent, pH and bovine serum albumin (BSA)

vishal  kachwal
@kachwal_vishal (https://twitter.com/kachwal_vishal)
Graduate Student at (BITS Pilani, Pilani campus) BIRLA INSTITUTE TECHNOLOGY AND SCIENCE, pilani, INDIA

Kachwal, Vishal, Parva Kumar Sharma, Amrit Sarmah, Shibasish Chowdhury, and Inamur Rahaman Laskar.

Abstract:

This  article  focuses  on  the  vital  role  of  hydrogen  bonding  to  explain  some  unusual  photophysical behaviors of an ‘Aggregation-induced emission’ (AIE) active Iridium( III ) complex. The preponderance of hydrogen  bonding  leads  to  the  complex’s  multifunctional  character,  viz.,  sensing  ability  of  base  and protein (BSA), pH probing, and solvatochromism. The  sensitivity  of  the  complex  to  BSA  was  measured  to  be  9.3  pM.

References, if applicable:

Kachwal, V., Sharma, P. K., Sarmah, A., Chowdhury, S., & Laskar, I. R, J.Mater. Chem. C, 2020, 8(19), 6605-6614.

Ruthenium(II) Polypyridine Complexes for Photodynamic Therapy: From In Silico Prediction to In Vivo Application

Johannes  Karges
@Johannes_Karges (https://twitter.com/johannes_karges)
Post-doctoral Fellow at University of California, San Diego, San Diego, USA

Prof. Gilles Gasser, Chimie ParisTech, PSL University, France; Prof. Hui Chao, Sun Yat-Sen University, China

Abstract:

The currently clinically applied photosensitizers are associated with many limitations. As an alternative, the use of Ru(II) polypyridine complexes from a theoretical DFT guided search to an in-depth photophysical and biological evaluation is presented. While being able to overcome all of the limitations, the lead compound demonstrated to eradicate a drug resistant tumour inside a mouse model upon clinically relevant 1-Photon or 2-Photon excitation.

References, if applicable:

1. J. Karges, S. Kuang, F. Maschietto, O. Blacque, I. Ciofini, H. Chao, G. Gasser, ChemRxiv 2020, DOI: 10.26434/chemrxiv.11767995.v1
2. J. Karges, S. Kuang, Y. C. Ong, H. Chao, G. Gasser, ChemRxiv, DOI: 10.26434/chemrxiv.12440012.v1.

Nuclear Medicine at War: Fighting Cancer

Jaspreet  Kaur
@jaspree75604402 (https://mobile.twitter.com/cic_cheminst)
Academia – Faculty/Staff at PCTE group of institute ludhiana, ludhiana, India

Dhandeep Singh

Abstract:

Little Boy and Fat Man, the two catastrophic bombs which caused the immense

destruction.Atomic

bombing killed large number of people in Hiroshima and Nagasaki.These bombs mutated

the gene system which caused the physical and genetically abnormalities. The most drastic after-effects of incident include the

development of cancer.The nuclear energy being harmful and dangerous in many ways but it is also

being used in a serviceable manner to cure a variety of diseases particularly cancer.

References, if applicable:

Jaspreet Kaur, Dhandeep Singh

Magnesium Cobaltates: Synthesis and Reactivity

John  Kelly
@TheWolf_Group (https://twitter.com/TheWolf_Group)
Post-doctoral Fellow at University of Regensburg, Regensburg, Germany

Abstract:

Generally, d-block metallates contain alkene or polyarene ligands and alkali metal cations, mainly lithium and potassium, yet the influence of these countercations on reactivity has been poorly explored. Our recent research has focused on d-block metallates stabilised by group 2 cations. Herein, we present the synthesis and structural characteristics of 2, the first magnesium complexes of the [Co(cod)2]- anion. The reactivity and coordination chemistry of these species will be discussed.

References, if applicable:

[1] Ellis, J. E.; Dalton Trans., 2019, 48, 9538

[2] Jonas, K.; Mynott, R.; Krüger, C.; Sekutowski, J. C.; Tsay, Y-H,; Angew. Chem. Int. Ed. Engl., 1976, 15, 767.

[3] (a) Hoidn, C. M.; Rodl, C.; McCrea-Hendrick, M. L.; Block, T.; Pöttgen, R.; Ehlers, A. W.; Power, P. P.; Wolf, R.; J. Am. Chem. Soc., 2018, 140, 13195. (b) Büschelberger, P.; Gӓrtner, D.; Reyes-Rodriguez, E.; Kreyenschmidt, F.; Koszinowski, K.; Jacobi von Wangelin, A.; Wolf, R.; Chem. Eur. J., 2017, 23, 3139. (c) C. M. Hoidn, T. M. Maier, K. Trabitsch, J. J. Weigand, R. Wolf, Angew. Chem. Int. Ed., 2019, 58, 18931. (d) C. Rödl, R. Wolf, Eur. J. Chem., 2019, 8332.

Three-in-one is really better: exploring the sensing and adsorption properties in a newly designed metal–organic system incorporating a copper (ii) ion

Mohammad Shahnawaz  Khan
@Sarcastickhan1 (https://twitter.com/Sarcastickhan1)
Graduate Student at Aligarh Muslim University, Aligarh, India

Mohd Khalid, Aligarh Muslim University, India

Abstract:

In this work we have successfully designed a 2-D copper(II) based coordination polymer for the functional applications. Fluorescence sensing property demonstrates the high selectivity and sensitivity towards nitrobenzene and Fe3+. Moreover, CP (1) acted as tremendous adsorbent material for natural dyes with different charges and size i.e. methylene blue (MB), methyl orange (MO) and rhodamine-B.

References, if applicable:

[1] Khan, M. S.; Khalid, M.; Ahmad, M. S.; Shahid, M.; & Ahmad, M.  Dalton Trans. 2019, 48, 12918.

[2] Nagarkar, S. S.; Joarder, B.; Chaudhari, A. K.; Mukherjee, S.; & Ghosh, S. K. Angew. Chem. 2013, 125, 2953.

Construction of photoresponsive coordination polymers for tuning electrical conductivity

Samim  Khan
@samim_2k (https://twitter.com/samim_2k?lang=en)
Post-doctoral Fellow at Aliah University, Kolkata, India

Shouvik Chattopadhyay and Mohammad Hedayetullah Mir

Abstract:

Coordination polymers (CPs) have recently been used for the fabrication of electronic devices. A Cu(II) CP (1) has been synthesized which exhibits response with visible light enabling repetitive switching of the photocurrent displaying substantial on–off ratio. Secondly, a Cd(II) based CP (2) has been synthesized which undergoes [2+2] cycloaddition reaction to generate dimerized CP (3). Compound 2 shows better charge transport property than 3, may be due to π•••π stacking interactions in 2.

References, if applicable:

1. Khan, S.; Halder, S.; Ray, P. P.; Herrero, S.; González-Prieto, R.; Drew, M. G. B.; Chattopadhyay, S.; Cryst. Growth Des. 2018, 18, 651.
2. Islam, S.; Datta, J.; Maity, S.; Dutta, B.; Khan, S.; Ghosh, P.; Ray P. P.; Mir, M. H.; Cryst. Growth Des. 2019, 19, 4057.

Bio-derived and Biodegradable Lignin-graft-Poly(lactic acid) Copolymers

Diana  Kim
@Diana_Chem (https://twitter.com/Diana_Chem)
Graduate Student at University of British Columbia, Vancouver, Canada

Hyuk-Joon Jung, Graduate Student, Canada; Love-Ese Chile, PhD, Canada; Addie Bahi, PhD, Canada; Frank Ko, Professor, Canada; Parisa Mehrkhodavandi, Professor, Canada

Abstract:

Lignin is the second most abundant bio-derived material on earth after cellulose. Nonetheless, this cheap and renewable material has been underutilized due to the complexity of its structure. In this study, we aim to functionalize lignin with controlled molecular weight and enantiopure biodegradable poly(lactic acid) (PLA).  The prepared PLA is successfully grafted to lignin via graft-to synthetic strategy and a series of lignin-graft-PLA copolymers are synthesized.

References, if applicable:

1. Novaes, E.; Kirst, M.; Chiang, V.; Winter-Sederoff, H.; Sederoff, R., Lignin and Biomass: A Negative Correlation for Wood Formation and Lignin Content in Trees. Plant Physiol. 2010, 154 (2), 555-561.
2. Iguchi, Y.; Akasaka, S.; Asai, S., Formation of PLA stereocomplex crystals during melt-blending of asymmetric PLLA/PDLA/PMMA blends of varying miscibility. Polym. J. 2020, 52 (2), 225-235.
3. Kadla, J. F.; Kubo, S.; Venditti, R. A.; Gilbert, R. D.; Compere, A. L.; Griffith, W., Lignin-based carbon fibers for composite fiber applications. Carbon 2002,40 (15), 2913-2920.
4. Johansson, C.; Bras, J.; Mondragon, I.; Nechita, P.; Plackett, D.; Simon, P.; Gregor Svetec, D.; Virtanen, S.; Giacinti Baschetti, M.; Breen, C.; Aucejo, S., Renewable Fibers and Bio-based Materials For Packaging Applications – A Review of Recent Developments. Bioresources 2012, 7 (2), 2506-2552.
5. Tsuji, H., Poly(lactide) Stereocomplexes: Formation, Structure, Properties, Degradation, and Applications. Macromol. Biosci. 2005, 5 (7), 569-597.
6. Sun, Y.; Yang, L.; Lu, X.; He, C., Biodegradable and renewable poly(lactide)–lignin composites: synthesis, interface and toughening mechanism. J. Mater. Chem. A 2015, 3 (7), 3699-3709.
7. Chile, L.-E.; Kaser, S. J.; Hatzikiriakos, S. G.; Mehrkhodavandi, P., Synthesis and Thermorheological Analysis of Biobased Lignin-graft-poly(lactide) Copolymers and Their Blends. ACS Sustainable Chem. Eng. 2018,6 (2), 1650-1661.
8. Yu, I.; Acosta-Ramírez, A.; Mehrkhodavandi, P., Mechanism of Living Lactide Polymerization by Dinuclear Indium Catalysts and Its Impact on Isoselectivity. 2012, 134 (30), 12758-12773.

Monoanionic pincer complexes of bismuth: potential new class of Lewis acid catalysts

Marcus Kindervater Bannon Kindervater
@mbkindervater (https://twitter.com/mbkindervater)
Graduate Student at Dalhousie University, Halifax, Canada

Dr. Saurabh Chitnis, Dalhousie University, Canada.  Toren Hynes, Dalhousie University, Canada. Katherine Marczenko, Dalhousie University, Canada.

Abstract:

Herein we debut the coordination chemistry of a rigid P2N3 phosphinimine and a flexible PNP pincer complex of bismuth that show varying degrees of planarity. We further demonstrate the ability for PNP-Bi complexes to support highly electrophilic Bi (III) centers with potential application as Lewis acid catalysts.

References, if applicable:

Kindervater, M. B.; Hynes, T.; Marczenko, K. M.; Chitnis, S. S. Dalt. Trans. 2020. https://doi.org/10.1039/D0DT01413C.

Structural Transformations of a Mechanochemically Generated Polymorphic Organocalciate

Ross F Koby
@rawssk0be (https://twitter.com/rawssk0be)
Graduate Student at Vanderbilt University, Nashville, United States

Ross F. Koby, Vanderbilt University, USA; Alicia M. Doerr, University of Tennessee, Knoxville, USA; Nicholas R. Rightmire, Vanderbilt University, USA; William W. Brennessel, University of Rochester, USA; Brian K. Long, University of Tennessee, Knoxville, USA; Timothy P. Hanusa, Vanderbilt University, USA

Abstract:

Ball milling K[A’] (A’ = [1,3-(SiMe3)2C3H3]-) with CaI2 yields [KCaA´3], which initially forms a structure (1) likely containing sigma-bound allyl ligands. Over time, the compound rearranges to a form (2) with eta 3-bound allyl ligands, which can be crystallized as a coordination polymer. The transformation from 1 to 2 can be followed by NMR and has been modeled with DFT calculations. Form 2 is capable of initiating polymerization of methyl methacrylate and isoprene at extremely low temperature.

References, if applicable:

The Rate of Cadmium Metallation of Metallothionein is Dependent on Structure and Binding Pathways

Natalie Christine Korkola
@NatalieKorkola (https://twitter.com/nataliekorkola)
Graduate Student at The University of Western Ontario, London, Canada

Daisy Wong, The University of Western Ontario, Canada; Martin Stillman, The University of Western Ontario, Canada

Abstract:

The protein metallothionein (MT) binds up to 7 divalent metals using 20 cysteines. [1] Metallation proceeds by either binding to terminal cysteines or through bridging “clusters”.[2] Here, the kinetics of these cadmium metallation pathways using stopped flow combined with UV-visible spectroscopy were studied. The beaded pathway proceeded much faster than the cluster pathway. Unfolding of apo-MT also slowed down the rate.[3] This provides a further understanding of MT’s metallation pathways.

References, if applicable:

1. Sutherland, D. E. K.; Stillman, M. J., The “magic numbers” of metallothionein. Metallomics 2011, 3, 444-463.
2. Irvine, G. W.; Pinter, T. B.; Stillman, M. J., Defining the metal binding pathways of human metallothionein 1a: balancing zinc availability and cadmium seclusion. Metallomics 2016, 8 (1), 71-81.
3. Wong, D. L.; Korkola, N. C.; Stillman, M. J., Kinetics of competitive Cd2+ binding pathways: the realistic structure of intrinsically disordered, partially metallated metallothioneins. Metallomics 2019, 11 (5), 894-905.

Combining Metal-Metal and Metal-Ligand Cooperativity Using a Naphthyridine-based Proton-responsive PNNP ‘Expanded pincer’

Errikos  Kounalis
@ErrikosKounalis (https://twitter.com/ErrikosKounalis)
Graduate Student at Utrecht University, Utrecht, The Netherlands

Martin Lutz, Utrecht University, The Netherlands     Daniël L. J. Broere, Utrecht University, The Netherlands

Abstract:

Inspired by nature, [1-2] we have synthesized a proton responsive ‘expanded pincer’ ligand that can bind multiple 1st-row transition metals in close proximity and facilitate metal-metal and metal-ligand cooperativity. We have demonstrated cooperative activation of H2 on a dicopper (I) complex, concomitant with the formation of a uniquely shaped Cu4H2 cluster. [3] Additionally, organocopper complexes and their remarkable structural behavior will be discussed. [4]

References, if applicable:

[1]  Sippel, D.; Rohde, M.;  Netzer, J.; Trncik, C.; Gies, J.; Grunau, K.; Djurdjevic, I.; Decamps, L.; Andrade, S.L.A,  Einsle, O. Science. 2020, 359, 6383, 1484-1489.

[2] Can, M.;  Armstrong, F.A.; Ragsdale, S.W. Chem. Rev. 2014, 114, 8, 4149–4174.

[3]  Kounalis, E.; Lutz, M.; Broere, D.L.J. Chem. Eur. J. 2019, 25, 58, 13280-13284.

[4] Kounalis, E.; Lutz, M.; Broere, D.L.J. Organometallics 2020, 39, 4, 585–592.

Autonomous Chemical Robot Discovers the Rules of Coordination Chemistry

Daniel J Kowalski
@dankowalskichm (https://twitter.com/dankowalskichm)
Graduate Student at University of Glasgow, Glasgow, UK

Luzian Porwol, University of Glasgow, UK / Alon Henson, University of Glasgow, UK / De-Liang Long, University of Glasgow, UK / Nicola Bell, University of Glasgow, UK / Leroy Cronin, University of Glasgow, UK

Abstract:

Digital chemistry is a rapidly growing discipline, although the adoption of automation has been slower in coordination chemistry than other areas. [1-3] We demonstrate the use of an unsupervised algorithm to robotically search a predefined chemical space for novel coordination complexes based on the data from in situ analysis. [4] Without any prior knowledge or simulation of chemistry, the algorithm has permitted the isolation of multiple new complexes and further in situ observations.

References, if applicable:

[1] Coley, C. W.; Eyke, N. S.; Jensen, K. F. Angew. Chem. Int. Ed. 2020, 59, ASAP

[2] Gromski, P. S.; Henson, A.; Granda, J.; Cronin L. Nat. Rev. Chem. 2019, 3, 119

[3] Henson, A. B.; Gromski, P. S.; Cronin L. ACS Cent. Sci. 2018, 4, 793

[4] Porwol, L.; Kowalski, D. J.; Henson, A.; Long, D.-L.; Bell, N. L.; Cronin L. Angew. Chem. Int. Ed. 2020, 59, 11256

Fused Inorganic Rings Containing Germanium and Boron Towards Hybrid Materials

Kelsie E Krantz
@kek_kelsie (https://twitter.com/kek_kelsie)
Graduate Student at University of Virginia, Charlottesville, United States

Sarah Weisflog, University of Virginia, USA; Nathan Frey, Mississippi State University, UVA; Diane Dickie, University of Virginia, USA; Charles Edwin Webster, Mississippi State University, USA; Robert J. Gilliard, Jr., University of Virginia, USA

Abstract:

The synthesis of highly conjugated organic molecules has advanced light emitting diodes and other electronic display technologies. By incorporating other p-block elements into organic systems, improved optoelectronic properties are achieved. This poster will highlight a new class of pyrene-fused N-heterocyclic germylenes which display extremely large twist angles. Additionally, the isolation, characterization, and photoluminescent properties of their boron analogues will also be discussed.

References, if applicable:

Krantz, K. E.; Weisflog, S. L.; Frey, N. C.; Yang, W.; Dickie, D. A.; Webster, C. E.; Gilliard, R. J. Jr.,  Chem. Eur. J. 2020, DOI: 10.1002/chem.202002118

Krantz, K. E.; Weisflog, S. L.; Yang, W.; Dickie, D. A.; Frey, N. C.; Webster, C. E., Gilliard, R. J. Jr., Chem. Commun. 2019, 55, 14954

Synthesis and Characterization of Heteroleptic Redox Active Bismuth  Dithiolene and Dithiolate Complexes

Viveka K Kulkarni
@KulkarniViveka (https://twitter.com/KulkarniViveka)
Undergraduate Student at Mount Allison University, Sackville NB, Canada

Glen Briand, Mount Allison University, Canada; Jason Masuda, Saint Mary’s University, Canada

Abstract:

Redox catalysis often feature toxic transition metal centers that can be harmful to both human health and the environment. Bismuth is a potential alternative due to its relatively low toxicity and cost, but does not possess accessible oxidation states. The current study focuses on the use of redox non-innocent ligands to impart redox activity on a heteroleptic bismuth complexes.  The synthesis and structural characterization of two bismuth 3,4-toluenedithiolate complexes is reported.

References, if applicable:

Dinuclear Reductive Elimination of H2 from an Ir(III)-H is Made Possible by Metal/Ligand Proton Tautomerism

Jonathan L Kuo
jonathanlkuo (https://twitter.com/JonathanLKuo)
Post-doctoral Fellow at University of Pennsylvania, Philadelphia, United States

Karen I. Goldberg, University of Pennsylvania, United States

Abstract:

We have synthesized a square-planar Ir(I) carbonyl compound bearing a protic bis-pyrazolatopyridine ligand. Additional ligands PPh3 or tBuPy induce tautomerism, where a ligand-based proton migrates to the metal forming an octahedral Ir(III)–H. In solution, the hydride undergoes the formal dinuclear reductive elimination of H2, generating the corresponding Ir(II) dimer. This is possible because the hydride establishes a [tBuPy] dependent equilibrium with its ligand protonated Ir(I) tautomer.

References, if applicable:

Heteroatom-Rich Ligands for Heavy Metal Sequestration

Jan-Willem  Lamberink
@JwLamberink (https://twitter.com/JwLamberink)
Graduate Student at Western University, London, Canada

Carmen Venier, Johanna M. Blacquiere, Paul J. Ragogna, Western University, Canada

Abstract:

Contamination of generated effluent with heavy metals is an issue that plagues many industries. The phosphane-ene reaction can generate phosphorus rich networks that are promising materials for heavy metal sequestration. Modification and study of cross-linkers provides crucial insight into the effectiveness of the overall material. These studies have led to the use of an underused methodology for P-H bond addition to C=N bonds, which can be utilized in the synthesis of heteroatom-rich polymers.

References, if applicable:

1. Barakat, M. A. Arab. J. Chem. 2011, 4(4), 361.
2. Cuthbert, T. et al. Catal. Sci. Technol. 2017, 7(13), 2685
3. Buckler, S. A.; Epstein, M. Tetrahedron. 1962, 18(11), 1221

Ligand-Assisted Volatilization and Thermal Stability in Mo(VI) Compounds

Michael A. Land
@MikeL4nd (https://twitter.com/MikeL4nd)
Graduate Student at Carleton University, Ottawa, Canada

Katherine Robertson, Saint Mary’s University, Canada; Seán Barry, Carleton University, Camada

Abstract:

Herein, we investigate the volatility and thermal stability of the parent bis(tert-butylimido)dichloromolybdenum(VI) compound, and the effect of neutral ligands including amines, phosphines, ethers, and an N-heterocyclic carbene. Their volatility and thermal stability are assessed using thermogravimetric analysis and differential scanning calorimetry, respectively [1]. The compounds have also been ranked using a Figure of Merit system [2] based upon observed thermal behavior.

References, if applicable:

[1] Land, M. A.; Robertson, K. N.; Barry, S. T. Organometallics, 2020, 39, 916.

[2] Griffiths, M. B. E.; Dubrawski, Z. S.; Bačić, G.; Japahuge, A.; Masuda, J. D.; Zeng, T.; Barry, S. T. Eur. J. Inorg. Chem. 2019, 15, 4927.

SOLUBILITY MEASUREMENTS OF STRONTIUM CARBONATE IN AQUEOUS AMMONIUM CHLORIDE FOR AQUEOUS EXTRACTION OF STRONTIUM CARBONATE FROM STRONTIUM MOLYBDATES

Andres Felipe Lara Contreras
@AndresLaraCo (https://twitter.com/AndresLaraCo)
Graduate Student at Department of Chemistry and Chemical Engineering – Royal Military College of Canada, Kingston, Canada

Emily Corcoran, Department of Chemistry and Chemical Engineering – Royal Military College of Canada, Canada ; Jennifer Scott, Department of Chemistry and Chemical Engineering – Royal Military College of Canada, Canada

Abstract:

Sr-Mo-O compounds are synthesized to understand the thermochemistry of nuclear fuels. The formation of SrCO3 can affect subsequent thermodynamic measurements. A solid-liquid SrCO3 extraction method has been developed using aqueous NH4Cl, which preserves the solid Sr-Mo-O phase intact. Given the lack of S-L equilibria data for the SrCO3 + NH4Cl + H2O system, a preliminary assessment of solubility limits in the temperature range 298 to 348 K and NH4Cl concentration of 0.25 to 2.00 M is presented.

References, if applicable:

Iron Coordination Complexes for Ultra-High Efficiency Monolayer Electrochromic Materials

Nadia O Laschuk
@laschuk_ (https://twitter.com/laschuk_)
Graduate Student at Ontario Tech University, Oshawa, Canada

Iraklii I. Ebralidze, Ontario Tech University, Canada; Olena V. Zenkina, Ontario Tech University, Canada

Abstract:

Terpyridine (tpy) coordinated to Fe(II) forms a coloured complex. Electrochemical oxidation from Fe(II) to Fe(III) under low potentials results in a reversible bleaching of the complex, known as electrochromic materials (ECMs). We synthesized and characterized a series of iron(II) bis(tpy) complexes, and then covalently attached them to novel conductive inorganic nanoparticle (NP) supports. Together, these created atom efficient ECMs with ultrahigh durability and high colouration efficiencies.

References, if applicable:

Laschuk, N.I.; Obua, A.; Ebralidze, I.I.; Fruehwald, H.M.; Poisson, J.; Egan, J.G.; Gaspari, F.; Naumkin, F.Y.; Easton, E.B.; Zenkina, O.V. ACS Appl. Electron. Mater. 2019, 1, 1705-1717.

Exploring Through-Bond and Through-Space Magnetic Communication in 1,3,2-Dithiazolyl Radical Complexes

Dominique  Leckie
@ladominiquee (https://twitter.com/ladominiquee)
Graduate Student at University of Windsor, Windsor, Canada

Nadia Stephaniuk, University of Windsor, Canada. Ana Arauzo, CSIC-Universidad de Zaragoza, Spain. Javier Campo, CSIC-Universidad de Zaragoza, Spain. Jeremy Rawson, University of Windsor, Canada.

Abstract:

The field of single molecule magnets (SMM) has provided access to systems in which individual bits of data can be stored at the molecular (nm and sub-nm) scale. The use of paramagnetic ligands has attracted attention to increase the spin ground state in polynuclear complexes. While ligands comprising heavier p-block elements have the potential to increase magnetic anisotropy. Here, we present the characterization of prototypical complexes of the thiazyl radical MBDTA with M(hfac)2.(1)

References, if applicable:

(1) Leckie, D.; Stephaniuk, N. T.; Arauzo, A.; Campo, J.; Rawson, J. M., Chem. Commun. 2019, 55 (66), 9849-9852.

2-(2′-Pyridyl)-4,6-diphenylphosphinine: A Chemically Non-Innocent Ligand Toward Iron(0) and Nickel(0)

Julia  Leitl
@julia_leitl (https://twitter.com/julia_leitl)
Graduate Student at Institute of Inorganic Chemistry, University of Regensburg, Regensburg, Germany

Michael Marquardt, FU Berlin, Germany; Christian Müller, FU Berlin, Germany; Robert Wolf, University of Regensburg, Germany

Abstract:

Phosphinines are versatile ligands for transition metals due to their special steric and electronic properties.[1] In this work, new iron(0) complexes [Cp*FeL]– (1-σ and 1-π, Cp* = C5Me5) containing the chelating ligand 2-(2′-pyridyl)-4,6-diphenylphosphinine (L) have been prepared and found to undergo facile reaction with CO2 under ambient conditions.[2] In contrast, L forms of a homoleptic phosphinine complex [Ni(L)2] (4) with a Ni(0) precursor, which shows reactivity toward phenyl halides.

References, if applicable:

1. P. L. Floch, Coord. Chem. Rev. 2006, 250, 627–681.
2. J. Leitl, M. Marquardt, P. Coburger, D. J. Scott, V. Streitferdt, R. M. Gschwind, C. Müller, R. Wolf, Angew. Chem. Int. Ed. 2019, 58, 15407–15411.

How Do Metal Ions Affect the Ability of a Flavonoid to Quench the Superoxide Anion Radical?

Tyra M Lewis
@siwelaryt (https://twitter.com/siwelaryt)
Undergraduate Student at Department of Forensic Science, Environmental and Life Sciences, Trent University, Peterborough, Canada

Sanela Martic, Department of Forensic Science, Environmental and Life Sciences, Trent University, Peterborough, ON, Canada

Abstract:

Quercetin (QCR) is a strong antioxidant against superoxide anion radical (SAR) (1). While biologically-relevant metal ions regulate SAR, their roles on activity of QCR is not fully understood. By using electrochemical method (2), the ability of Fe(III) and Cu(II) to modulate QCR activity was measured for metal ion:QCR ratio and complex type. Data indicated that antioxidant ability of QCR was regulated by metal ion, whilst the Cu(II)-QCR complex exhibited greatest antioxidant activity with SAR.

References, if applicable:

1. Gil, E.S.; Couto, R.O. Braz. J. Pharmacogn. 2013, 23 (3), 542.
2. Zabik, N.L.; Anwar, S.; Ziu, I.; Martic-Milne, S. Electrochim. Acta. 2019, 296, 174.

Mesoionic N-heterocyclic olefin carbene tautomerization

Qiuming  Liang
@WalterQLiang (https://twitter.com/WalterQLiang)
Graduate Student at University of Toronto, TORONTO, Canada

Kasumi Hayashi, University of Toronto, Canada; Datong Song, University of Toronto, Canada

Abstract:

N-heterocyclic olefins (NHOs), sometimes referred to as deoxy-Breslow intermediates, have been widely studied and found broad applications in coordination chemistry and (organo)catalysis. We herein present an unprotected mesoionic N-heterocyclic olefins (mNHO) which can tautomerize into mesoionic carbenes (MIC) at room temperature. Experimental and computational studies allow us to compare their thermodynamic properties. An unusual O2 activation will also be presented.

References, if applicable:

Mechanism of 8-Aminoquinoline Directed Ni-Catalyzed C(sp3)-H Functionalization: Unanticipated Mononuclear and Dinuclear Paramagnetic Ni(II) Species.

Jun Yang  Liu
@ljyangjun (https://twitter.com/ljyangjun)
Graduate Student at University of Windsor, Windsor, Canada

Samuel Johnson, University of Windsor, Canada

Abstract:

The catalytic activation of C–H bonds using first row transition metals has been an ideal choice in constructing new C–C bonds, but first row metal such as Ni, is less reactive/selective. A common strategy is using directing groups(8-AQ). Although a wide range of Ni-catalyzed C–H activations are reported, studies probing the mechanisms remain limited.  This study aims at identifying catalytically-relevant key intermediates, and describing the mechanism of directed nickel-catalyzed C–H arylation.

References, if applicable:

Polymeric pH-Activated Nanoparticles for Lipo-toxic Cell Application

Kaitlynn M Lopes
@klvettegirl715 (https://twitter.com/klvettegirl715)
Graduate Student at Boston University, Boston, United States

1. Jialiu Zeng, Department of Chemistry Boston University, USA 2. Mark Grinstaff, Department of Biomedical Engineering Boston University, USA

Abstract:

Non-alcoholic fatty acid liver disease (NAFLD) is characterized by cellular lipotoxicity, increased lysosomal pH, and inhibited autophagic processes. We propose the development of polymeric pH-activated nanoparticles for acid delivery to the lysosomes within lipo-toxic cells. Nanoparticles with an average diameter of approximately 100 nm and a polydispersity between 0.1 and 0.2 were deemed ideal for cellular uptake. Optimal nanoparticles were formed and determined to be non-cytotoxic.

References, if applicable:

1. Younossi, Z., Anstee, Q.M., Marietti, M, Hardy, T., Henry, L., Eslam, M., George, J., & Bugianesi, E. Nature Reviews Gastroenterology & Hepatology. 2018, 15,11–20.
2. Trudeau, K.M., Colby, A.H., Zeng, J., Las, G., Feng, J.H., Grinstaff, M.W., Shirihai, O.S. J Cell Biol. 2016, 214 (1), 25-34.
3. Feldstein, A.E., Werneburg, N.W., Canbay, A., Gicciardi, M.E., Bronk, S.F., Rydzewski, R., Burgart, L.J., Gores, G.J. AASLD. 2004, 40 (1), 185-194.
4. Turro; N.J. and Lei, X. Langmuir. 1995, l (1), 2525-2533.

Tellurium-Containing Polymers for Organic Electronics

Bruno T. Luppi
@luppi_bruno (https://twitter.com/luppi_bruno)
Graduate Student at University of Alberta, Edmonton, Canada

Bruno T. Luppi, University of Alberta, Canada; Robert McDonald, University of Alberta, Canada; Michael J. Ferguson, University of Alberta, Canada; Lingzi Sang, University of Alberta, Canada; Eric Rivard, University of Alberta, Canada.

Abstract:

The field of polymer electronics often relies on complex molecular/polymeric structures and metastable device architectures to achieve high-performance.[1,2] This poster describes the synthesis of structurally simple Te-containing polymers of interest for photovoltaics.[3] These show reduced band gaps (e.g. 1.3 eV) when compared to their structurally analogous polythiophenes.[4] Additionally, cycloalkyl-fused oligomers reveal a drastic band gap reduction when the cycloalkyl ring size is altered.

References, if applicable:

1. L. Dou, Y. Liu, Z. Hong, G. Li and Y. Yang, Chem. Rev. 2015, 115, 12633.
2. L. Lu, T. Zheng, Q. Wu, A. M. Schneider, D. Zhao and L. Yu, Chem. Rev., 2015, 115, 12666.
3. B. T. Luppi, D. Majak, M. Gupta, E. Rivard and K. Shankar, J. Mater. Chem. A, 2019, 7, 2445.
4. B. T. Luppi, R. McDonald, M. J. Ferguson, L. Sang and E. Rivard, Chem. Commun., 2019, 55, 14218.

Benzene Insertion into a Nickel Hydride Bond

Casper M Macaulay
@eTheR_ealCasper (https://twitter.com/eTheR_ealCasper)
Post-doctoral Fellow at Dalhousie University, Halifax, Canada

Madhu Samolia, Brigham Young University, USA; Michael Ferguson, University of Alberta, Canada; Orson Sydora, Chevron Phillips Chemical Company Ltd., USA; Daniel Ess, Brigham Young University, USA; Mark Stradiotto, Dalhousie University, Canada; Laura Turculet, Dalhousie University, Canada

Abstract:

Treatment of (PN)NiNHDipp (PN = N-phosphinoamidinate ligand) with Me2PhSiH in benzene solvent yielded the crystallographically characterized, antifacial-coordinated, dinuclear species (PN)Ni(μ2–η3:η3-C6H8)Ni(PN) (1), representing the first isolated example of benzene insertion into a Ni–H bond. Efforts to generate (1) via β-hydride elimination of alkyl complexes instead afforded low-coordinate agostic alkyl complexes, including (PN)Ni(Neopentyl), the first neutral Ni(II) γ-agostic alkyl complex.

References, if applicable:

1. Macaulay, C. M.; Samolia, M.; Ferguson, M. J.; Sydora, O. L.; Ess, D. H.; Stradiotto, M.; and Turculet, L. Dalton Trans. 2020, 49, 4811-4816.

Synthesis of sterically hindered 9-phosphatriptycenes and computational investigation of their properties

Damien  Mahaut
@DMahautChem (https://twitter.com/DMahautChem)
Graduate Student at University of Namur, Namur, Belgium

Lei Hu, University of Namur, Belgium; Raphaël Robiette, Catholic University of Louvain-La-Neuve, Belgium; Benoît Champagne, University of Namur, Belgium; Guillaume Berionni, University of Namur, Belgium

Abstract:

Frustrated Lewis Pairs (FLPs) consist in bulky Lewis acid and base which cannot form a Lewis adduct because of steric repulsions and have been extensively used as transition metal-free catalysts for hydrogenations.[1] In this context, 9-phosphatriptycenes constitute promising Lewis bases due to their cage-like structures. In this poster, the synthesis of sterically hindered 9-phosphatriptycenes will be presented as well as a DFT investigation of their properties and potential for FLP chemistry.

References, if applicable:

1a. Stephan, D. W., Science 2016, 354, 1248.

1b. Lam, J.; Szkop,  K. M.; Mosaferi, E.; Stephan, D. W.; Chem. Soc. Rev. 2019, 48, 3592.

Photophysical and Optical Properties of Semiconducting Polymer Nanoparticles Prepared from Hyaluronic Acid and Polysorbate

Aleena  Malik
@amalik283 (https://twitter.com/amalik283)
Undergraduate Student at Univeristy of Windsor, Windsor, Canada

Gage Mason, University of Windsor, Canada. Dr Simon Rondeau Gagne, University of Windsor, Canada.

Abstract:

Diketopyrrolopyrrole-based semiconducting polymer nanoparticles prepared from hyaluronic acid and polysorbate were prepared and characterized using transmission electron microscopy, dynamic light scattering, small-angle neutron

scattering, and optical spectroscopy to determine their photophysical and optical properties. These nanoparticles were found to exhibit characteristics that are similar to the native polymers and show promise for application in biomedical imaging and nanomedicine.

References, if applicable:

S-S antioxidant assessment

Basel  Mansour
@BaselMa42697042 (https://twitter.com/BaselMa42697042)
Graduate Student at University of Windsor, Windsor, Canada

N/A

Abstract:

the assessment of the antioxidant activity of different compounds contains S-S bond by using computational methods

References, if applicable:

Bismuthanyl-Stibanes: The first neutral Bi-Sb σ-bonds

Kate M Marczenko
@KMMarczenko (https://twitter.com/KMMarczenko)
Graduate Student at Dalhousie University, Halifax, Canada

Saurabh Chitnis, Dalhousie University, Canada

Abstract:

Thermally-robust bismuthanylstibanes are prepared in a one-step, high yield reaction, providing the first examples of neutral Bi–Sb σ-bonds in the solid state. DFT calculations indicate that the bis(silylamino)naphthalene scaffold is well-suited for supporting otherwise labile bonds. The reaction chemistry of the Bi–Sb bond is exploited by showing insertion of a sulfur atom, providing the first documented example of a Bi–S–Sb bonding moiety.

References, if applicable:

Dendronized Side Chains in Conjugated Polymers Toward More Robust Organic Electronics

Gage  Mason
@magegason (https://twitter.com/magegason)
Graduate Student at University of Windsor, Windsor, Canada

Aleena Malik, University of Windsor, Canda: Simon Rondeau-Gagne, University of Windsor, Canada

Abstract:

Organic semiconductors are used in organic electronics due to their solution processability and optoelectronic properties. Efforts have been made to improve the mechanical properties and solubility while enhancing stability. Several methodologies have been utilized to improve these properties, but sidechain engineering remains one of the most efficient. Recently, our group has incorporated dynamic bonding moieties (ligands or hydrogen bonding) to improve the thermomechanical properties.

References, if applicable:

1. Heeger, A. J. et al. Adv. Mater. 2014, 26, 2993−2998.
2. Hou, J. et al. Chem. Mater. 2014, 26, 3603−3605.
3. Bazan, G. C. et al. Angew. Chem., Int. Ed. 2014, 53, 14378−14381.
4. Brabec, C. J. et al. Adv. Funct. Mater. 2014, 24, 1449−1457.
5. Andreasen, J. W. et al. J. Mater. Chem. A 2015, 3, 17022−17031.
6. Tian, W. et al. Sol. Energy Mater. Sol. Cells 2012, 97, 28−33

Synthetic Efforts Towards Biologically Active Chelated Boron Complexes

Kathleen L May
@khem4may (https://twitter.com/khem4may)
Graduate Student at Ryerson Univeristy, Toronto, Canada

Robert A. Gossage, Steven A. Westcott

Abstract:

Boron-containing compounds have been overlooked when considering drug design. More recently popularized by the discovery of 5-fluorobenzoxaborole, boron-containing compounds have seen increased use and research interest. We intend to take advantage of the known biological activity of various azoles and use them with those a boron centre to increase biological efficacies. Ligand synthesis and advancements as well as future directions to determine their biological activity will be noted.

References, if applicable:

Nickel-Catalyzed Cross-Coupling of Sulfonamides With (Hetero)aryl Chlorides

Ryan T McGuire
@_mcguireryan (https://twitter.com/_McGuireRyan)
Graduate Student at Dalhousie University, Halifax, Canada

Connor M. Simon, Dalhousie University, Canada

Abstract:

The development of Ni-catalyzed C-N cross-couplings of sulfonamides with (hetero)aryl chlorides is reported. These transformations, which were previously achievable only with Pd catalysis, are enabled by use of air-stable (L)NiCl(o-tol) pre-catalysts (L=PhPAd-DalPhos and PAd2-DalPhos), without photocatalysis. The collective scope of (pseudo)halide electrophiles demonstrated herein is unprecedented for any reported catalyst system for sulfonamide C-N cross-coupling.

References, if applicable:

McGuire, R. T.; Simon, C. M.; Yadav, A. A.; Ferguson, M. J.; Stradiotto, M. Angew. Chem. Int. Ed. 2020, 59, 8952-8956.

Computational Studies on the Formation of Biological Per/Polysulfides

Paul  Meister
@meisterp3 (https://twitter.com/meisterp3/)
Graduate Student at University of Windsor, Windsor, Canada

JamesWGauld, University of Windsor, Canada

Abstract:

Sulfur is a rare element in biology and typically exists as one of two proteinogenic amino acids, cysteine and methionine. They have important roles in redox signaling, protein folding, and enzymatic function. Persulfides (RSSH) are reactive intermediates making them a difficult topic to study. Herein, we used computational methods to study the formation of persulfide bonds and the extension of a sulfur chain within sulfide:quinone oxidoreductase (SQR) from a hyperthermoacidophilic archaea.

References, if applicable:

Probing the Sequence of Copper-Thiolate Cluster Formation in Metallothionein Using Native ESI-Mass Spectrometry

Adyn  Melenbacher
@adynmelenbacher (https://twitter.com/adynmelenbacher)
Graduate Student at The University of Western Ontario, , London

Martin Stillman

Abstract:

Cu is vital for life. Free cellular Cu catalyzes the formation of dangerous radicals. Cellular copper chaperones are required to avoid uncontrolled redox chemistry. Metallothionein (MT) binds Zn(II) and Cu(I). ESI-MS can be used to view the series of Cu(I)-thiolate clusters forming in MT, however it is unclear which cysteines bind to the Cu(I) first. Isolated domain fragments of MT have been used to determine domain preference of Cu(I) binding through detailed native ESI-MS studies.

References, if applicable:

Scheller, J. S.; Irvine, G. W.; Wong, D. L.; Hartwig, A.; Stillman, M. J. Metallomics. 2017, 9, 447.

Mechanistic Investigation of the Nickel-Catalyzed Carbonylation of Alcohols

Maximilian  Menche
@maxmenche (https://twitter.com/maxmenche)
Graduate Student at Catalysis Research Laboratory (CaRLa), , Germany

Abstract:

The carbonylation of alcohols represents an atom-efficient methodology for the preparation of carboxylic acids. Current processes either rely on harsh reaction conditions or precious metals[1-2]. Here, we present a mechanistic study of a catalytic system based on NiI2, which can regioselective carbonylate benzylic alcohols. Quantum-chemical computations were used to evaluate the underlying mechanistic processes. They revealed that two mechanisms are responsible for the observed reactivity.[3]

References, if applicable:

[1] Samel, U.; Kohler, W.; Gamer, A. O.; Keuser, U.; Yang, S.; Jin, Y.; Lin, M.; Wang, Z. Propionic acid and derivatives in Ullmann’s Encyclopedia of Industrial chemistry, Wiley-VCH, Weinheim, 2014.

[2] Elango, V.; Murphy, M. A.; Smith, B. L.; Davenport, K. G.; Mott, G. N.; Moss, G. L. Process for producing ibuprofen. EP0284310A1, 1988.

[3] Sabater, S.; Menche, M.; Ghosh, T.; Krieg, S.; Rück, K. S. L.; Paciello, R.; Schäfer, A.; Comba, P.; Hashmi, A. S. K.; Schaub, T. Mechanistic Investigation of the Nickel-Catalyzed Carbonylation of Alcohols. Organometallics 2020, 39, 870–880.

Exploring the photocatalytic hydrogen production by ruthenium polypyridine  and cobaloxime assemblies

AB QAYOOM MIR
@mir_qayoom (https://twitter.com/InorgChem)
Undergraduate Student at IIT GANDHINAGAR, BARAMULLA, India

Jaya Bhartia  Ab Qayoom Mir and Arnab Dutta*

Abstract:

Axial coordinated imidazole derivatives; such as

imidazole carboxylic acids and histidine; directly

linked an identical Co(dimethylglyoxime)2 core is

shown to catalyze the reduction of aqueous proton to

hydrogen (H2) in light-driven photocatalytic reactions

in water near neutral pH. When we used [Ru(bpy)3]

2+

References, if applicable:

Sustainable Synthesis of Pyridines, Quinolines and Pyrimidines by Ru Catalyzed Acceptorless Dehydrogenation of Alcohols and C-C/C-N Coupling

Rajarshi  Mondal
@JuchemMondal (https://twitter.com/JuchemMondal)
Post-doctoral Fellow at University of Manitoba, Winnipeg, Canada

Issiah B. Lozada, PhD candidate, Canada; Olha Stotska, B.Sc. student, Ukraine; Dr. David E. Herbert, Associate Professor, Canada

Abstract:

The acceptorless dehydrogenation of widely available biomass generated alcohols followed by coupling with amines can lead to sustainable and atom economical routes to core organic building blocks including nitrogen-containing heterocycles. In this presentation, preparation of a simple novel P^N ligand based Ru catalyst for acceptorless dehydrogenation of alcohols, substrate scope for N-heterocycle synthesis such as pyridines, quinolines and photo-emissive pyrimidines will be discussed [1].

References, if applicable:

[1]. (a) Mondal, R.; Herbert, D. E. Organometallics 2020, 39, 1310 (b) Mondal, R.; Lozada, I.B.; Davis, R. L.; Williams, J. A. G.; Herbert, D.E. Inorg. Chem. 2018, 57, 4966 (c) Mondal, R.; Giesbrecht, P. K.; Herbert, D. E. Polyhedron 2016, 108, 156.

Development of Green Solvent Processable Semiconductors for Printed Electronics

Madison  Mooney
@Madison77772905 (https://twitter.com/Madison77772905)
Graduate Student at University of Windsor, Windsor, Canada

Simon Rondeau-Gagne, University of Windsor, Canada

Abstract:

Our research aims to minimize the impact of electronic waste on the environment by developing a series of green solvent processable organic semiconductors for Printed Electronics. By incorporating hydrogen-bonding saccharide moieties through side-chain engineering, a series of semiconducting polymers were synthesized to be soluble in environmentally-friendly alcohol-based solvents, rather than the toxic halogenated solvents typically used for processing of these materials.

References, if applicable:

A fluorine transfer reaction: C-F bond activation leading to nucleophilic fluorination

Patrick  Morgan
@azure_wanderer (https://twitter.com/azure_wanderer)
Graduate Student at University of Nottingham, Nottingham, United Kingdom

Andrew C. Marr, Queen’s University Belfast, United Kingdom; Pete Licence, University of Nottingham, United Kingdom

Abstract:

We present a first account of a transfer fluorination protocol where fluorine is transferred from a perfluorinated moiety onto a non-fluorinated substrate. The reaction occurred via the concurrent C–F bond activation, fluorine transfer, and C–F bond formation resulting in selective fluorination of an organic target. Fluorine transfer was tracked using in-situ ReactIR, where the rate of C-F bond activation was observed to match the rate of C-F bond formation.

References, if applicable:

(1)          Morgan, P. J.; Hanson-Heine, M. W. D.; Thomas, H. P.; Saunders, G. C.; Marr, A. C.; Licence, P. Organometallics 2020, 39 (11), 2116–2124.

The Influence of Carbon Donor Ligands on Biomimetic High-Spin Iron Complexes for N2 Reduction

Alexandra L Nagelski
@ANagelski (https://twitter.com/ANagelski)
Graduate Student at Yale University, New Haven, United States

Majed S. Fataftah, Melissa M. Bollmeyer, Sean F. McWilliams, Samantha N. MacMillan, Brandon Q. Mercado, Kyle M. Lancaster, and Patrick L. Holland

Abstract:

The active site clusters of nitrogenase enzymes have a C-based bridge between high-spin Fe sites. We present functional and structural models to elucidate the impacts of carbon and sulfide donors in simpler Fe compounds. This includes Fe alkyl and alkylidene complexes capable of reducing N2 to NH3 (with protons and electrons). We report the first diiron complex bridged by alkylidene and sulfide ligands, which models part of the active-site cluster (FeMoco) in the resting state of Mo-nitrogenase.

References, if applicable:

Halogen Bonding as a Structure-Directing Interaction in Dithiadiazolyl Radicals

Mitchell A Nascimento
@MitchellNas (https://twitter.com/MitchellNas)
Graduate Student at University of Victoria, Victoria, Canada

Elodie Heyer, University of Windsor, Canada. Robert Less, Cambridge University, United Kingdom. Christopher Pask, Cambridge University, United Kingdom. Ana Arauzo, University of Zaragoza, Spain. Javier Campo, University of Zaragoza, Spain. Jeremy Rawson, University of Windsor, Canada.

Abstract:

We report dithiadiazolyl radicals p-XC6F4CNSSN (X = Br (1) or I (2)). 1 is polymorphic, comprising pure diamagnetic π*−π* dimers, fully monomeric radicals, and mixtures of each. 2 is isomorphous to 1α. Both Br and I groups in 1 and 2 promote sigma-hole interactions of the type C−X···N (X = Br, I), reflecting the strength of this interaction in heavier halo-derivatives. A subtle competition of halogen/nitrogen and sulfur/nitrogen bonds directs structure and is examined through DFT methods.

References, if applicable:

1. Nascimento, M. A.; Heyer, E.; Less, R. J.; Pask, C. M.; Arauzo, A.; Campo, J.; Rawson, J. M. Cryst. Growth Des. 2020, 20, 4313.

Olefin metathesis performance is impacted by X group reactivity in WOR3X/SiO2 catalysts

Chris  Nicholas
@CatalysisChris (https://twitter.com/CatalysisChris)
Industry at Honeywell UOP, Des Plaines, United States

Abstract:

The novel complex W(=O)Np3F has been synthesized and characterized by fluorination of the corresponding chloride counterpart with AgBF4. Reaction with SiO2 proceeds both through silanolysis and opening of a siloxane bridge thanks to the affinity of silicon for fluoride. This material presenting fluorine on its surface shows an enhanced catalytic activity in propylene self-metathesis in comparison to its monopodal counterpart (≡SiO)W(=O)Np3.

References, if applicable:

1. Merle, N.; Mazoyer, E.; Szeto, K.C.; Rouge, P.; De Mallmann, A.; Berrier, E.; Delevoye, L.; Gauvin, R.M.; Nicholas, C.P.*; Basset, J.-M.*; Taoufik, M.* J. Organomet. Chem. 2018, 869, 11-17.
2. Merle, N.; Girard, G.; Popoff, N.; De Mallmann, A.; Bouhoute, Y.; Trébosc, J.; Berrier, E.; Paul, J.-F.; Nicholas, C.P.; Del Rosal, I.; Maron, L.*; Gauvin, R.M.*; Delevoye, L.*; Taoufik, M.* Inorg. Chem. 2013, 52, 10119-30.
3. Mazoyer, E.; Merle, Nicolas; de Mallmann, A.; Basset, J.-M.*; Berrier, E.; Delevoye, L.; Paul, J.-F.; Nicholas, C. P.; Gauvin, R. M.*; Taoufik, M.* Chem. Commun. 2010, 46(47), 8944-8946.

Imparting Multifunctionality by Utilizing Biporosity in a Zr-Based MOF

Pranay Pravin Ninawe
@000pranay (https://twitter.com/000pranay)
Undergraduate Student at Indian Institute of Science Education and Research, Pune, India

Ashwini Jadhav, Kriti Gupta, Nirmalya Ballav, Indian Institute of Science Education and Research, Pune, India

Abstract:

An elegant design strategy of selectively incorporating conducting polymers in a bi-porous Metal-Organic Framework was introduced, which resulted in decoupled electrical and thermal conductivities. This process led to loading of ~12 wt% of polymers inside the pores. Electrical conductivity was enhanced by ~10^6 times in the nanocomposites bringing them into semiconducting regime, along with a significant decrease in thermal conductivity, as well as simultaneous porosity retention up to ~70%.

References, if applicable:

Jadhav, A.; Gupta, K.; Ninawe, P.; Ballav, N. Angew. Chem. Int. Ed. 2020, 59, 2215.

Activation of Ammonia and Hydrazine via the Formation of Terminal Fe(III) Amido and Imido Radical Intermediates

Lucie  Nurdin
@lucie_nurdin (https://twitter.com/lucie_nurdin)
Graduate Student at University of Calgary, Calgary, Canada

Yan Yang, Warren E. Piers, Laurent Maron, Michael L. Neidig, Benjamin S. Gelfand

Abstract:

Herein, we explore the use of a dianionic pentadentate ligand B2Pz4Py reported by our group [1,2] for the activation of NH3. We hypothesized that this robust and electronically rich ligand could help to stabilize higher oxidation state complexes. In particular, we sought to detect terminal Fe(III)NH2 and Fe(IV)NH complexes as they have been proposed as key intermediates of ammonia oxidation to N2, and could provide mechanistic insights to improve catalyst design using earth abundant metals [3].

References, if applicable:

[1] Spasyuk, D. M.; Carpenter, S. H.; Kefalidis, C. E.; Piers, W. E.; Neidig, M. L.; Maron, L. Chem. Sci. 2016, 7, 5939.

[2] Nurdin, L.; Spasyuk, D. M.; Fairburn, L.; Piers, W. E.; Maron, L. J. Am. Chem. Soc. 2018, 140, 16094.

[3] Zott, M. D.; Garrido-Barros, P.; Peters, J. C. ACS Catal. 2019, 9, 10101.

Biodegradable electronics: Ionic diode based on a cellulose nanocrystals-agarose hydrogel

Kudzanai  Nyamayaro
@KudziNyamayaro (https://twitter.com/KudziNyamayaro)
Graduate Student at University of British Columbia, Vancouver, Canada

Parya Keyvani, UBC, Canada. Francesco D’Acierno, UBC, Canada. Carl A. Michal, UBC, Canada. John D. W. Madden, UBC, Canada. Savvas G. Hatzikiriakos, UBC, Canada. and Parisa Mehrkhodavandi, UBC, Canada.

Abstract:

Herein, we employ cellulose nanocrystals to fabricated a polyelectrolyte gel diode capable of rectifying ionic current.  The current rectification ratio reaches 70 reproducibly, which is significantly higher than analogous diodes generated with microfibrillated cellulose (~15) and olefin based polyelectrolyte gel diode (~40). The current voltage characteristics of the CNC-hydrogel diode were influenced by concentration, gel thickness, scanning frequency, and applied voltage.

References, if applicable:

1. Zhang, W.; Zhang, X.; Lu, C.; Wang, Y.; Deng, Y., J. Phys. Chem. C 2012, 116 (16), 9227-9234.
2. Cayre, O. J.; Chang, S. T.; Velev, O. D., J. Am. Chem. Soc. 2007, 129 (35), 10801-10806.

Covalent Rigidification of Self-assembled Electroactive Materials with Polydiacetylenes

Audithya N Nyayachavadi
@anyayach (https://twitter.com/anyayach)
Graduate Student at University of Windsor, Windsor, Canada

1. Nazir Tahir, S. Holger Eichhorn, Simon Rondeau-Gagné

Abstract:

Well-defined self-assembly of organic materials is an efficient strategy to control the optoelectronic properties of organic materials. However, supramolecular self-assembly are sometimes unstable and difficult to process. Here, we discuss our new approach to covalently stabilize self-assembled organic materials by incorporating diacetylenes capable of polymerizing in the solid state, preserving morphologies while tuning the optoelectronic properties of the resulting materials.

References, if applicable:

1. Tahir, M.N.; Nyayachavadi, A.; Morin, J.-F.; Rondeau-Gagné, S. Polym. Chem. 2018, 9, 3019.
2. Nyayachavadi, A.; Langlois, A.; Tahir, M. N.; Billet, B.; Rondeau-Gagné, S. ACS Appl. Polym. Mater. 2019, 1, 1918.
3. Tahir, M.N.; Abdulhamied, E.; Nyayachavadi, A.; Selivanova, M.; Eichhorn, S.H.; Rondeau-Gagné, S. Langmuir. 2019, 47, 15158.

Computational Design of Fluorescent Chemosensors for Mercury Detection:  Binding Affinities of Metal Ions with Thiacrown Ether

Meagan S Oakley
@meaganoakley (https://twitter.com/meaganoakley)
Post-doctoral Fellow at University of Minnesota, Minneapolis, United States

Shakiba Azimi, Department of Chemistry, University of Alberta, Canada, Mariusz Klobukowski, Department of Chemistry, University of Alberta, Canada

Abstract:

Design and improvement of fluorescence-based chemosensors for the detection of heavy metals remains a challenge. We have studied the BODIPY-benzothiacrown chemosensor[1] which showed selective chelation-enhanced fluorescence to the Hg2+ metal ion. We computationally investigated the selectivity of the chemosensor as a positive fluorescent sensor for the Hg2+ metal, as well as considering other crown ethers and other metal ions in order to understand what drives the selectiveness of the crown.

References, if applicable:

[1] Kim, H.-J.; Kim, S.-H.; Kim, J.-H.; Lee, E.-H.; Kim, K.-W.; Kim, J. S. Bull.  Korean Chem. Soc. 2008, 29, 1831–1834.

Pyrazine as Noncovalent Conformational Locks in Semiconducting Polymers for Enhanced Charge Transport and Stability in Thin Film Transistors

Michael U Ocheje
michocheje (https://twitter.com/michocheje)
Graduate Student at University of Windsor, Windsor, Canada

Michael Ocheje, University of Windsor, Canada; Renée Goodman, University of Windsor, Canada; Lenaic Soullard, ENSCBP, France; Mah-Noor Malik, University of Windsor, Canada; Mhadu Yadiki, University of Windsor, Canada; Simon Rondeau-Gagné, University of Windsor, Canada

Abstract:

A backbone engineering was performed on highly rigid semiconducting polymers based on diketopyrropyrrole (DPP) units to include pyrazine-containing moieties. Their utilization in bottom-gate bottom-contact devices and their potential to act as ligands for coordinating metals highlights the capacity of this new semiconductor for fully printed high-performance electronics.

References, if applicable:

Ocheje, MU; Goodman, RB; St. Onge, PBJ; Malik, MN; Yadiki, M; He, Y; Tao, Y; Chu, TY; Rondeau-Gagné, S J. Mat. Chem. C, 2019, 7, 11507

Synthesis of bis(imidazolium) salts with dimethylene benzene linkers

Elisa M Olivas
@ElisaOlivas4 (https://twitter.com/ElisaOlivas4)
Undergraduate Student at Cal Poly Pomona, Bryn Mawr, United States

Jacob P. Brannon California State Polytechnic University United States, Dr Chantal Stieber California State Polytechnic University United States

Abstract:

Bidentate N-heterocyclic carbene (NHC2) ligands are of interest as strongly sigma-donating ligands to metals. Previous work illustrates NHC2 ligands with primarily ethylene and methylene linkers. This work focuses on synthesis of conjugated (bis)imidazolium salts by reacting mesitylimidazole with 1,2-di(bromomethyl) benzene or 1,2-dibromo-2-phenylethane in toluene. Characterization was with X-ray diffraction and 1H NMR. The NHC2 with 1,2-di(bromomethyl) benzene was successfully synthesized.

References, if applicable:

Hopkinson, M. N.; Richter, C.; Schedler, M.; Glorius, F. An Overview of N-Heterocyclic Carbenes. Nature 2014, 510 (7506), 485–496

Luminescent Difluoroboron Complexes Supported by Phenanthridine-Based β-Ketoiminates

Robert J Ortiz
@OrtizRobert44 (https://twitter.com/OrtizRobert44)
Undergraduate Student at University of Manitoba, Winnipeg, Canada

Issiah B. Lozada, University of Manitoba, Canada. David E. Herbert, University of Manitoba, Canada.

Abstract:

Difluoroboron complexes have shown potential for developing cheaper materials for light emitting devices. Our group has developed synthetic methodologies that enable us to incorporate phenanthridine into various ligand frameworks, with their coordination complexes exhibiting interesting photophysical properties. Incorporating phenanthridine into β-ketoimines enabled us to isolate novel difluoroboron β-ketoiminates with photophysical properties dependent on the substituent on the phenanthridine.

References, if applicable:

Controlled Generation of 9‐Boratriptycene by Lewis Adduct Dissociation: Accessing a Non‐Planar Triarylborane

Arnaud  Osi
@ArnaudOsi (https://twitter.com/ArnaudOsi)
Graduate Student at UNamur, Namur, Belgique

Aurélien Chardon UNamur, Belgium, Damien Mahaut, UNamur, Belgium, Guillaume Berionni, UNamur, Belgium.

Abstract:

The 9‐boratriptycene was generated in solution by protodeboronation of a tetra‐aryl boron ate complex with HNTf2. We studied its stereoelectronic properties by quantifying its association with Lewis bases. Beyond the high pyramidalization of the 9‐boratriptycene and its low reorganization energy upon coordination, theoretical calculations revealed that the absence of π-donation from the triptycene aryl rings to the boron vacant pz orbital is the main reason for its high Lewis acidity.

References, if applicable:

Chardon, A.; Osi, A.; Mahaut, D.; Doan, T.-H.; Tumanov, N.; Wouters, J.; Fusaro, L.; Champagne, B.; Berionni, G. Angew. Chem. Int. Ed. 2020, DOI: 10.1002/anie.202003119

Boranes and Alanes: Novel Synthesis and Lactonisation

Darren M. C. Ould
@darren_ould (https://twitter.com/darren_ould?lang=en)
Graduate Student at Cardiff University, , Wales

Micol Santi, Cardiff University, Wales. Thomas Wirth, Cardiff University, Wales. Rebecca L. Melen, Cardiff University, Wales.

Abstract:

Triaryl boranes have proven to be highly successful in catalysing organic reactions.[1,2] In this work the use of a series of triarylboranes to undergo metal-free lactonization of diazo compounds is presented, while also showing how tuning the Lewis acidity of the borane centre is important.[3] From here the synthesis and structural properties of a series of novel triarylalane species are discussed, highlighting key differences in the chemistry between triarylboranes and triarylalanes.[4]

References, if applicable:

[1] Lawson, J. R.; Melen, R. L.  Inorg. Chem. 2017, 56, 8627.

[2] Jupp, A. R. and Stephan, D. W., Trends Chem., 2019, 1, 35.

[3] Santi, M.; Ould, D. M. C.; Wenz, J.; Soltani, Y.; Melen, R. L.; Wirth, T. Angew. Chem. Int. Ed., 2019, 58, 7861.

[4] Ould, D. M. C.; Carden, J. L.; Melen, R. L. manuscript under revision.

Convenient Access to Germanium and Aluminium Compounds Using The Pendant Power of Methyl-pyridinato Ligand

SANJUKTA  PAHAR
@PaharSanjukta (https://twitter.com/PaharSanjukta)
Graduate Student at CSIR-NATIONAL CHEMICAL LABORATORY, Pune, India

Sakya Singha Sen, Principal Scientist, CSIR-National Chemical Laboratory, Pune-India

Abstract:

A methyl-pyridine side arm in the nacnac, leads to a tridentate ligand (2,6-iPr2-C6H3NC(Me)CHC(Me)NH(CH2py)).We have synthesized and characterized  chlorogermylene which undergoes unusual smooth ring contraction in presence of Lewis acid (GeCl2) via C–N bond cleavage, facile dehydrocoupling and 6 membered Al-heterocycle. With another Lewis acid,AlCl3, leads to the formation of dicholoaluminim complex via the transmetallation. Crystal reveals pyridine coordinates to the  Al.

References, if applicable:

1. Xu, X.; Chen, Y.; Zou, G.; Sun, J. Single. Dalton Trans. 2010, 39, 3952−3958
2. Pahar. S.; V.S.V.S.N. Swamy.; Das. T.; Gonnade. R. G.; Vanka. K.; Sen, S. S.; Manuscript under preparation

Reactivity of Dioxygen and Nitric oxide towards  Nonheme  Diiron(II)-hydrosulfide Complex

Nabhendu  Pal
@nabhendupal (https://twitter.com/Nabhendupal)
Graduate Student at Indian association for the cultivation of science, Kolkata, India

Abstract:

While attempted synthesis of diiron(II)-hydrosulfide complexes using HS−produced insoluble precipitate, Reaction of Fe(BF4)2•6H2O, Et3N, and HN-Et-HPTB with RSH (R = PhCH2,tBu) /NaStBu in DMF at RT yielded the desired complex.  The dioxygen activity of 1a to generate an oxygenated diiron complex at low temperature and its subsequent decomposition at RT has been examined.  The reaction of  1a with 6 eq. Ph3CSNO produces [Fe2(N-Et-HPTB) (SH)(NO)2(DMF)](BF4)2.

References, if applicable:

Pal.N; Majumdar. A; Dalton Trans. 2019, 48, 5903-5908.

High-throughput screening of MOF catalysts

Joseph M Palomba
@PeriodiKangeroo (https://twitter.com/PeriodiKangeroo)
Graduate Student at UC San Diego, San Diego, United States of America

Mark Kalaj, UC San Diego, USA; Brian Pimentel, UC San Diego, USA; Steven Harvey, CCDC Chemical Biological Center, USA; Jared DeCoste, CCDC Chemical Biological Center, USA; Gregory Peterson, CCDC Chemical Biological Center, USA; Seth Cohen, UC San Diego, USA

Abstract:

Metal-organic frameworks (MOFs) are microporous hybrid materials whose metal and organic components make them useful heterogeneous catalysts for chemical transformations. MOFs combine the recyclability of heterogeneous materials with active site tailoring akin to homogeneous catalysts. We developed a high-throughput screening (HTS) method to examine >100 MOFs and MOF-polymer composites. This HTS method was tested on chemical warfare agent simulants to probe a broad spectrum of chemical space.

References, if applicable:

Rh(I) and Rh(III) pincer complexes: (R,R)-Ph-pybox vs iPr-PNP

Gemma L Parker
@GemmaParker0110 (https://twitter.com/GemmaParker0110)
Graduate Student at University of Warwick, Coventry, United Kingdom

Samantha Lau, University of Warwick, U.K.; Baptiste Leforestier, University of Warwick, U.K.; Adrian B Chaplin, University of Warwick, U.K.

Abstract:

Pincer ligands are frequently used in organometallic chemistry and can be readily adapted, enabling the steric and electronic properties of metal derivatives to be tuned.(1) However, the impact of such changes can be difficult to gauge in a quantitative manner. To this end, we present our work investigating the rhodium(I) and rhodium(III) carbonyl fragments as probes for the donor properties of pincer ligands, exploiting convenient spectroscopic handles.(2)

References, if applicable:

1. E. Peris and R. H. Crabtree, Chem. Soc. Rev., 2018, 47, 1959–1968.
2. G. L. Parker, S. Lau, B. Leforestier and A. B. Chaplin, Eur. J. Inorg. Chem., 2019, 3791–3798.

Heavy main-group carbonyl-alkyne metathesis

Löwe  Pawel
@PawelLoewe (https://twitter.com/PawelLoewe)
Graduate Student at Westfälische Wilhelms-Universität Münster, Münster, Germany

Milica Feldt, Westfälische Wilhelms-Universität Münster, Germany; Marius A. Wünsche, Westfälische Wilhelms-Universität Münster, Germany; Lukas F. B. Wilm, Westfälische Wilhelms-Universität Münster, Germany; Fabian Dielmann, Westfälische Wilhelms-Universität Münster, Germany.

Abstract:

On this poster we show that oxophosphonium ions, which are the isoelectronic phosphorus congeners to carbonyl compounds, undergo [2+2] cycloaddition reactions with different terminal alkynes to generate cationic 1,2-oxaphosphetes. This new compound class was isolated and structurally characterized.

The strained phosphorus-oxygen heterocycles open to the corresponding hetero-diene structure at elevated temperature, which was used to generate six-membered phosphorus heterocycles.

References, if applicable:

9826. Löwe, M. Feldt, M. A. Wünsche, L. F. B. Wilm, F. Dielmann J. Am. Chem. Soc. 2020, 142, 21, 9818-9826.

How Does Milstein’s Catalyst Really Work?

John  Pham
@jjrpham (https://twitter.com/jjrpham)
Undergraduate Student at Colgate University, Hamilton, NY, United States

Eamon Reynolds, Colgate University, United States Tianyi He, Colgate University, United States John Buttner, Colgate University, United States Jack Malek, Colgate University, United States Jason Keith, Colgate University, United States Anthony Chianese, Colgate University, United States Fernando Carbajal, Colgate University, United States Cole Jarczyk, Colgate University, United States Sophie Kelly, Colgate University, United States Thao Kim, Colgate University, United States

Abstract:

Mechanistic proposals of Milstein’s ruthenium pincer catalyst for ester hydrogenation have relied on reversible deprotonation of a methylene linker of the pincer ligand. Here, we present evidence that under catalytic conditions, Milstein’s catalyst undergoes ethane loss followed by hydrogen addition to give an active catalyst containing an N-H group. This newly discovered activated form is the most efficient catalyst for ester hydrogenation, giving over 10,000 turnovers at rt with no added base.

References, if applicable:

Conversion of amine from aromatic nitro compounds using Heterogeneous catalyst

Ariprasanth  Ramalingam
Ariprasanth 4 (https://mobile.twitter.com/ARIPRASANTH4)
Graduate Student at SRM University, Chennai, India

Samaraj Elavarasan. Department of chemistry, SRM institute of science ad technology, Kattankullathur,    Chennai-603203

Abstract:

The reduction of aromatic nitro compound to amines is an important organic transformation.  As amines are necessary for preparation of dye, drugs, herbicides, and pesticides and preparation of amines received great attention Here we demonstrate the synthesis of amines from nitro compounds using base metal catalysts. The catalysts were thoroughly investigated by a series of characterization techniques such as XRD, TEM, SEM, and XPS.

References, if applicable:

Stabilization and significance of group 14 metallylenes

Ravindra Krushnaji Raut
@ravindraraut19 (https://twitter.com/ravindraraut19)
Graduate Student at Indian Institute of Science Education and Research, Pune, Pune, India

Moumita Majumdar, Associate Professor, Indian Institute of Science Education and Research, Pune.

Abstract:

The heavier analogues of carbene are unique due to its one unoccupied and another lone pair orbital, which can mimic the transition metals. The stabilization of such challenging species either requires steric protection by bulky ligand or kinetic stabilization by extra donor group in ligand. Here, we have stabilized neutral and cationic forms of germylenes and stannylene in simple Schiff base multidentate ligands. The unusual reactivity is displayed in the current poster.

References, if applicable:

Cationic Alkyl-Indium Complexes: Tuning the Reactivity with Hemilability

Hootan  Roshandel
@hootan_r (https://twitter.com/hootan_r)
Undergraduate Student at University of British Columbia, Vancouver, Canada

Chatura Goonesinghe, Graduate Student (PhD), Canada  Hyuk Joon Jung, Graduate Student (PhD), Canada  Carlos Diaz, Graduate Student (PhD), Canada  Kudzanai Nyamayaro, Graduate Student (PhD), Canada  Maria Ezhova, Academia (Research Assistant), Canada  Parisa Mehrkhodavandi, Academia (Professor), Canada

Abstract:

Although widely used to tune the chemistry of transition metals, there are only a handful of reported hemilabile systems that explore the reactivity of group-13 metals. Thus, based on previous work in our group, we developed a series of cationic alkyl-indium complexes containing a heterocyclic hemilabile side-arm, providing the first glance at using hemilability to significantly influence the reactivity of indium complexes towards the ring opening polymerization of epoxides and rac-lactide.

References, if applicable:

1. Jung, H.-J.; Chang, C.; Yu, I.; Aluthge, D. C.; Ebrahimi, T.; Mehrkhodavandi, P., ChemCatChem 2018, 10 (15), 3219–3222.
2. Diaz, C.; Ebrahimi, T.; Mehrkhodavandi, P.. Chem. Commun. 2019, 55 (23), 3347–3350.

Computational Insight into the Sulfilimine (S=N) Bond Formation in Collagen-IV.

Anupom  Roy
@Anupom88 (https://twitter.com/Anupom88)
Graduate Student at University of Windsor, Windsor, Canada

James W. Gauld, Associate Professor, University of Windsor, Ontario, Canada

Abstract:

Collagen IV is an essential component of the basement membrane in the tissues. It provides proper cellular structure by the formation of sulfilimine bond (S=N) between Methionine and Lysine or Hydroxylysine (cross-links) residues which can be formed with or without post-translational modification. The aim of the study is the investigation of the formation of sulfilimine bond and its nature in Collagen IV using multi-scale approach that included MD, QM-Cluster, QT-AIM, and NBO analysis.

References, if applicable:

1. Ronsein, G.E., Winterbourn, C.C., Di Mascio, P. and Kettle, A.J. Free Radical Biology and Medicine, 2014, 70, 278-287.
2. Vanacore, R., Ham, A.J.L., Voehler, M., Sanders, C.R., Conrads, T.P., Veenstra, T.D., Sharpless, K.B., Dawson, P.E. and Hudson, B.G. Science 2009 325, 1230-1234.

Electrically Conductive and Photosensitive Heteronuclear Complexes: From Binuclear to Tetranuclear to Coordination Polymers.

Sourav  Roy
@souravscott (https://twitter.com/souravscott)
Post-doctoral Fellow at Indian Institute of Science, , India

Abstract:

Recently inorganic-organic hybrids are found to be useful for the fabrication of active electronic devices.1-4 Two Ni/Pb, one Co/Na and one Co/Hg/Na Schiff base complexes are prepared and their electrical properties are investigated which show significant on–off ratio when used as photo-switch. Unique supramolecular networks [C-H•••π(N3) and S•••Br interactions] are observed in the complexes which can modulate the electrical conductivities.5

References, if applicable:

1) Dey, A.; Layek, A.; Roychowdhury, A.; Das, M.; Datta, J.; Middya, S.; Das, D.; Ray, P. P. RSC Adv. 2015, 5, 36560.

2) Roy, S.; Halder, S.; Drew, M. G. B.; Ray, P. P.; Chattopadhyay, S. New J. Chem. 2018, 42, 15295.

3) Roy, S.; Halder, S.; Drew, M. G. B.; Ray, P. P.; Chattopadhyay, S. ACS Omega 2018, 3, 12788.

4) Roy, S.; Dey, A.; Ray, P. P.; Ortega-Castro, J.; Frontera, A.; Chattopadhyay, S. Chem. Commun. 2015, 51, 12974.

5) Conesa-Egea, J.; Redondo, C. D.; Martínez, J. I.; Gomez-Garc ́ía, C. J.; Castillo, Ó.; Zamora, ́ F.;  Amo-Ochoa, P. Inorg. Chem. 2018, 57, 7568.

Photocatalytic hydrogen evolution under red light using ruthenium(II) 2,4-di(pyridin-2-yl)-pyrimidine complexes as photosensitizers

Mira Theresa Rupp
@MiraRupp (https://twitter.com/MiraRupp)
Graduate Student at Université de Montréal, Universitaet Wuerzburg, Montréal, Canada

Thomas Auvray, Université de Montréal, Canada; Natali Shevchenko, Université de Montréal, Canada; Lukas Swoboda, Universitaet Wuerzburg, Germany; Dirk Kurth, Universitaet Wuerzburg, Germany; Garry Hanan, Université de Montréal, Canada

Abstract:

A series of non-symmetric 2,6-di(pyridin-2-yl)-pyrimidine ligands with peripheral pyridine substituents in different positions and their Ru(II) complexes are reported. They exhibit a red-shifted emission, longer excited-state lifetimes and higher luminescence quantum yields and are easier to reduce than analogous terpyridine (tpy) complexes. In H2 evolution experiments under blue and red light, the complexes are more active but less stable than previously reported [Ru(tpy)2]2+ photosensitizers.

References, if applicable:

Synthesis and Reactivity of a Terminal Gallium Imide

Artemis M Saddington
@artemis_sadd (https://twitter.com/artemis_sadd)
Undergraduate Student at University of Oxford, Oxford, United Kingdom

Megan Edwards, University of Oxford, U.K. Andreas Heilmann, University of Oxford, U.K. Caitilin McManus, University of Oxford, U.K. Jamie Hicks, University of Oxford, U.K. Jose Goicoechea, University of Oxford, U.K. Simon Aldridge, University of Oxford, U.K.

Abstract:

The potassium gallyl complex K2[(NON)Ga]2 (NON = 4,5-bis(2,6-diisopropylanilido)-2,7-ditertbutyl-9,9-dimethylxanthene) acts as a source of nucleophilic gallium. The reaction of K2[(NON)Ga]2 with the bulky azide Ph3SiN3 enables the isolation of a terminal gallium imide species. The imide contains a highly polarised Ga-N bond, enabling reaction with PhCCH, PhSiH3, PhCHO, CO2, N2O and CO.

References, if applicable:

1. Hicks, J.; Vasko, P.; Goicoechea, J. M.; Aldridge, S. Nature 2018, 557, 92–95.
2. Heilmann, A.; Hicks, J.; Vasko, P.; Goicoechea, J.; Aldridge, S. Angew. Chemie 2020, 132, 4927–4931.

Commodity Polymers to Functional Materials: Single Step Synthesis via Hydroaminoalkylation

Sabrina S Scott
@sabselscott (https://twitter.com/sabselscott)
Graduate Student at University of British Columbia, Vancouver, Canada

Sorin-Claudiu Rosca, University of British Columbia, Canada; Damon J. Gilmour, University of British Columbia, Canada, A2O Materials INC, Canada; Pat Brant, A2O Materials INC, Canada; Laurel L. Schafer*, University of British Columbia, Canada, A2O Materials INC, Canada

Abstract:

In an effort to improve the accessibility of functional materials, vinyl terminated polypropylene was aminated via the atom-economic hydroaminoalkylation transformation in solvent free conditions. This work provides an inexpensive and resource conscious protocol to access mono-telechelic polymers with amine functionality, providing an alternative to the typical multi-step syntheses often coupled with protection/deprotection procedures which fail to meet modern demands for “green” products.1-5

References, if applicable:

1. J. Y. Dong, Z. M. Wang, H. Hong and T. C. Chung, Macromolecules, 2002, 35, 9352–9359.
2. S. Ji, T. R. Hoye and C. W. Macosko, Polymer (Guildf)., 2008, 49, 5307–5313.
3. A. A. Nagarkar, A. Crochet, K. M. Fromm and A. F. M. Kilbinger, Macromolecules, 2012, 45, 4447–4453.
4. S. Pal, F. Lucarini, A. Ruggi and A. F. M. Kilbinger, J. Am. Chem. Soc., 2018, 140, 3181–3185.
5. M. Alizadeh and A. F. M. Kilbinger, Macromolecules, 2018, 51, 4363–4369.

Electronic structure investigation of electron rich and deficient Cu-salen complexes

Anmol  Sharma
@anmol98z (https://twitter.com/anmol98z)
Undergraduate Student at University of the Fraser Valley, Abbotsford, Canada

Abstract:

Metal complexes coordinated by salen ligands have attracted much attention due to their highly tunable nature and consequently diverse application in catalysis and medicinal purposes.[1-3] This poster will discuss the synthesis of three novel Cu-salen complexes and characterization via IR, UV-Vis, and NMR spectroscopies. The electronic structure of the target compounds, investigated by cyclic voltammetry, will also be discussed.

References, if applicable:

1 – Chiang, L., Herasymchuk, K., Thomas, F., Storr, T., Inorg. Chem., 2015, 54, 5970−5980

2 – Kanso, H., Clarke, R. M., Kochem, A., Arora, H., Philouze, C., Jarjayes, O., Storr, T., Thomas, F., Inorg. Chem., 2020, 59, 5133−5148

3 – Bellefeuille, D., Orio, M., Barra, A., Aukauloo, A., Journaux, Y., Philouze, C., Ottenwaelder, X., Thomas, F., Inorg. Chem., 2015, 54, 9013−9026

Oligonuclear Ru(II) Assemblies Based on Ditopic Terpyridine Ligands

Natali  Shevchenko
@NataliShevche15 (https://twitter.com/NataliShevche15)
Undergraduate Student at Université de Montréal, Montréal, Canada

Mira Rupp

Abstract:

Linear polytopic terpyridine ligands can form rod-type assemblies when complexed with metal ions like ruthenium and iron. In this study, ditopic terpyridine ligands are synthesized, complexed and characterized. Tertbutyl groups are introduced to the ligands to increase the solubility of long supramolecular assemblies in organic solvents. The complex’s absorption and redox potentials are studied and compared to an iron complex of the monotopic terpyridine ligand with tertbutyl substituents.

References, if applicable:

1. T. Auvray, R. Sahoo, D. Deschênes, G. S. Hanan, Dalton Transactions, 2019, 48, 15136-15143
2. Wang, J.; Hanan, G. S. Synlett, 2005,36 (41), 1252-1254
3. D. J. Díaz, S. Bernhard, G. D. Storrier, H. D. Abruña, The Journal of Physical Chemistry B, 2001, 105, 8746-8754.
4. M. Rupp, M. Sc. thesis, University of Wuerzburg, 2018
5. Laramée-Milette, B. M.Sc. Thesis; Université de Montréal, 2013
6. Nagy, E.M.; Pettenuzzo, A.; et al. Chemistry- A European Journal, 2012, 18(45), 14464-14472
7. B. Laramée-Milette, G. S. Hanan, Chemical Communications, 2017, 53, 10496-10499

Terphenyl(bisamino)phosphines as Ligands in Gold-Catalysis

Jan-Erik  Siewert
@siewert_jan (https://twitter.com/siewert_jan)
Undergraduate Student at LIKAT Rostock, Rostock, Germany

André Schumann, Malte Fischer, Christoph Schmidt, Dr. Christian Hering-Junghans

Abstract:

Terphenyl(bisamino)phosphines have been identified as effective ligands in cationic gold(I) complexes for the hydroamination of acetylenes. These systems are related to Buchwald phosphines and their steric properties have been evaluated. Effective hydroamination was noted even at low catalyst loadings and a series of cationic gold(I) complexes has been structurally characterized clearly indicating stabilizing effects through gold-arene interactions.

References, if applicable:

1. D. S. Surry, S. L. Buchwald, Angew. Chem., Int. Ed. 2008, 47, 6331.
2. D. Malhotra , M. S. Mashuta , G. B. Hammond, B. Xu , Angew. Chem., Int. Ed. 2014, 53, 4456.
3. T. Witteler, H. Darmandeh, P. Mehlmann, F. Dielmann, Organometallics 2018, 108, 3064.
4. S. Ullrich, B. Kovačević, X. Xie, J. Sundermeyer, Angew. Chem. Int. Ed. 2019, 58, 1033.
5. W. Petz, F. Weller, J. Uddin, G. Frenking, Organometallics 1999, 18, 619.
6. R. Dorta, E. D. Stevens, N. M. Scott, C. Costabile, L. Cavallo, C. D. Hoff, S. P. Nolan, J. Am. Chem. Soc. 2005, 127, 2485.
7. C. A. Tolman, Chem. Rev. 1977, 77, 313.
8. L. Falivene, R. Credendino, A. Poater, L. Serra, R. Oliva, V. Scarano, L. Cavallo, Organometallics 2016, 35, 2286.

Cytotoxic activity studies against non-tumorigenic HEK293 and cancer HEPG2 cell lines by  Vanadium (V) compounds

Aniela Montserrat Silva Nolasco
anni_nolasco (https://twitter.com/anni_nolasco)
Graduate Student at Universidad Juárez Autónoma de Tabasco, Tabasco, México

Luz Camacho, Instituto Nacional de Pediatría, México; Omar Saavedra, Universidad Juárez Autónoma de Tabasco, México; Oswaldo Hernández, Universidad Juárez Autónoma de Tabasco, México; Ignacio León, CEQUINOR (CONICET UNPL), Argentina;  Irma Sánchez, Universidad Juárez Autónoma de Tabasco, México

Abstract:

Recent studies have established the ability of decavanadates that contain amine-based ligands and/or cations to exert different biological effects in vitro and in vivo. 1-3 In this study the cytotoxic activity studies against non-tumorigenic HEK293 human embryonic kidney cells and human liver cancer HEPG2 cells (IC 50 values) were performed for sodium decavanadate, metforminium decavanadate, sodium metavanadate and metformin hydrochloride in a concentration range of 10-100 μM.

References, if applicable:

1. Rehder, D. Future Med. Chem. 2012, 4, 1823-1837.
2. Aureliano, M. World J. Biol. Chem. 2011, 2, 215-225.
3. Sigel, A; Freisinger, E; Roland K. O. Metal Ions in Life Sciences. Berlin, Germany, 2019; Vol.19. www.mils-WdG.com https://doi.org/10.1515/9783110527872-008.
4. Sánchez, I. et al. EurJIC. 2014, 27, 4581.

Analysis of Solid-State Geometries and Ground-State Energies of Tin-Containing Complexes via DFT

Kaitlyn  Silverthorne
@silverthornekt (https://twitter.com/silverthornekt)
Undergraduate Student at Ryerson University, Toronto, Canada

Daniel Foucher, Ryerson University, Canada

Abstract:

Polystannanes are of interest due to their low band-gap and semi-conductive properties. Several monomeric precursors have been synthesized and characterized via NMR (119Sn) spectroscopy and single-crystal XRD. My project focuses on analyzing these tin-containing small molecules via DFT to assess the accuracy of various functionals in predicting solid-state geometries and ground-state energies of both the open and hypercoordinate conformations of these complexes.

References, if applicable:

1. Pau, J.; D’Amaral, G. M.; Lough, A. J.; Wylie, R. S.; Foucher, D. A. Chem. Eur. J. 2018, 24, 18762-18771

Iron catalyzed hydroboration of alkenes and alkynes

Arpita  Singh
@Arpita1391 (https://twitter.com/Arpita1391)
Graduate Student at Texas Tech University, Lubbock, United States

Abstract:

Iron complexes [BIAN]Fe(I)(η6‐toluene) and [BIAN]FeCl2 (BIAN=bis(2,6‐diisopropylaniline)acenaphthene) have been employed in the selective reduction of alkynes and alkenes via hydroboration. The hydroboration of alkynes and alkenes in the presence of HBpin and an activator at 70 °C afforded linear vinyl and alkyl boronic esters, respectively. Selectivity up to 98% was observed for alkyl boronic esters and exclusive formation of trans product was observed for vinyl boronic esters.

References, if applicable:

Small Molecule Activation by Transition Metal Polyhydride Clusters

Kathleen  Snook
asexualchemist1 (https://twitter.com/asexualchemist1)
Undergraduate Student at Boston University, Boston, United States

Cathlene Del Rosario, Boston University, United States; Lenorah Stott, Boston University, United States; John Caradonna, Boston University, United States

Abstract:

Polyhydride transition metal clusters introduce a new type of catalyst with multiple reactive metal surfaces, reservoirs of electron density, and fluxional hydride ligands. We are investigating the topology of an open butterfly cluster [M4(μ3-X)2(μ-X)5X4]n- along with the hexatungsten clusters [W6(µ3-Cl)8Cl6]2- and [W6(µ-Cl)12Cl6]2-. Successful syntheses of these clusters are confirmed by Raman and 183W NMR spectroscopy, and SCXD studies.

References, if applicable:

1. Energy Environ. Sci. 2010, 3 (7), 884-890.
2. Global Biogeochemical Cycles. 2019, 33, 318-342.
3. Energy Fuels. 2009, 23 (4), 1874-1887.
4. Catal. Sci. Technol. 2016, 6 (12), 4048-4058.
5. J. Am. Chem. Soc. By Mol. Met. Clust. 1982, 104 (21),

5630-5633.

6. Inorganic Syntheses; Girolami, G.S., Sattelberger, A.P.,

Eds.; John Wiley & Sons, Inc., 2014; Vol. 36, pp 19-23.

7. J. Am. Chem. Soc. 1995, 117 (31), 8139-8150.

A Responsive-at-Metal Cyclometalated Platinum Luminophore

Miguel A. Soto
@Miguel_A_Soto_ (https://twitter.com/Miguel_A_Soto_)
Post-doctoral Fellow at The University of British Columbia, Vancouver, Canada

Miguel Soto, University of British Columbia, Canada; Veronica Carta, University of British Columbia, Canada; Ryan Andrews, University of British Columbia, Canada; Mohammad Chaudhry, University of British Columbia, Canada; Mark. J. MacLachlan, University of British Columbia, Canada

Abstract:

Molecular emitters are very valued as they are used in a range of applications and technologies. When designing an emitter, there are three characteristics that are highly desirable to control: emitted color, emission decay, and quantum yield, which are adjusted through the selection of a metal core, and by the covalent modification of a ligand. Here, I will discuss how simple solvent molecules can get the job done by modulating non-covalent interactions in cyclometalated Pt(II) complexes

References, if applicable:

Soto, M. A.; Carta, V.; Andrews, R. J.; Chaudhry, M. T.; MacLachlan, M. J., Angew. Chem. Int. Ed. 2020, 59, 10348

Tuning the Redox Properties of MnI-NHC Complex Through Remote Coordination Approach

Anandi  Srinivasan
@AnandiSrinivas1 (https://twitter.com/AnandiSrinivas1)
Post-doctoral Fellow at Laboratoire d’Electrochimie Moléculaire LEM, Paris, Paris, France

Anandi Srinivasan, Université de Paris, Laboratoire d’Electrochimie Moléculaire (LEM), CNRS, 75013 Paris, France, Jesús Campos, Université de Paris, Laboratoire de Chimie et Biochimie Pharmacologiques et Toxicologiques, UMR CNRS 8601, Paris, France, Nicolas Giraud, Instituto de Investigaciones Químicas (IIQ), Consejo Superior de Investigaciones Científicas (CSIC) and University of Sevilla. Avenida Américo Vespucio, 49, 41092 Sevilla, Spain, Marc Robert, Université de Paris, Laboratoire d’Electrochimie Moléculaire (LEM), CNRS, 75013 Paris, France and Institut Universitaire de France (IUF),75005 Paris, France, Orestes Rivada‒Wheelaghan* Université de Paris, Laboratoire d’Electrochimie Moléculaire (LEM), CNRS, 75013 Paris, France.

Abstract:

Modulating the electronics and reactivity of transition metal complexes by incorporating alkali metal substituents offers a powerful strategy for enhancing the performance electrocatalysts. Along these lines, we present the correlation of remote interactions of different alkali cations with the novel MnI‒complex, 1, and its effects on the redox behavior of Mn center. Additionally, the electrochemical behavior of 1 towards CO2, including the effects of added alkali salts will be presented

References, if applicable:

Optimizing Semiconducting Materials Through M-L Interactions.

Blake Joseph St. Onge
@Stonge912 (https://twitter.com/stonge912)
Graduate Student at University of Windsor, Windsor, Canada

Abstract:

Metal-Ligand (M-L) interactions in materials chemistry which involve the incorporation of side-chain engineering in semiconducting π-conjugated polymers have become an increasingly popular field of study. Our work concludes that utilizing semiconducting π-conjugated polymers with pincer ligands in the sidechains can incorporate Fe(II) centers which demonstrate an increase in device performance and mobilities.

References, if applicable:

10. B. St.Onge, T. Chen, A. Langlois, A. Younus, I. Jo Hai, B. Lin, Y. Chiu and S. Rondeau-Gagné, J. Mater. Chem. C, 2020, DOI: 10.1039/D0TC01536A.

C-C Bond Formation Reactions Using B(C6F5)3

Katarina  Stefkova
@KatarinaStefko1 (https://twitter.com/KatarinaStefko1)
Graduate Student at Cardiff University, Cardiff, United Kingdom

Rebecca Melen, Cardiff University, UK

Abstract:

The poster demonstrates the recent developments in B(C6F5)3 catalysed alkenylations as well as it shows the utilization of B(C6F5)3 with PMes3 as Frustrated Lewis Pairs in higly stereoselective C-C bond formation to obtain E- alkenes from readily available styrenes.

References, if applicable:

Soltani, Y.; Dasgupta, A.; Stefkova, K. et al., CPRS, 2020, 1.

Dasgupta, A.; Stefkova, K. et al., DOI: 10.1002/anie.202007176.

Synthesis of Redox Active Organoindium Dithiolate Catalysts

Alexander Hubert Stöckli
@HubertStockli (https://twitter.com/HubertStockli)
Undergraduate Student at Mount Allison University, Sackville, NB, Canada

Glen Briand, Mount Allison University; Jason Masuda, Saint Mary’s University

Abstract:

Traditional redox catalysts use precious transition metals and tend to produce toxic waste. Use of relatively non-toxic indium as a metal centre in these compounds would help alleviate this problem. However, indium has limited redox activity on its and so the use of a redox active ligand is needed. This work seeks to synthesize redox active indium compounds with varied physical properties. The synthesis and structural characterization of a novel indium 3,4-tolueneditholate complex is reported.

References, if applicable:

C(sp2)−C(sp2) homo-dimerization of a pincer scaffold: A synergistic experimental and computational study supports binuclear Ni(III)−Ni(III) mechanisms

1. Maryamdokht Taimoory Nazanin Taimoory
   @NTaimoory (https://twitter.com/NTaimoory)
   Post-doctoral Fellow at University of Michigan, Chemistry Department, Ann Arbor, USA

Pronay Roy, Melanie S. Sanford

Abstract:

Chemical transformations promoted by bimetallic systems are abundant in nature and catalytic processes.1,2

This presentation will highlight our ongoing studies on of the key role of bimetallic Ni(III)−Ni(III) complexes in mediating the C(sp2)−C(sp2) reductive elimination on a catalytically relevant, quinoline-benzamide scaffold.

References, if applicable:

1. Lindahl, et. al. J. Inorg. Biochem. 2012, 106, 172.
2. a) Diao et. al. J. Am. Chem. Soc. 2016, 138, 4779; b) Diao et. al. Angew.Chem. Int. Ed. 2016, 55,7534; c) Uyeda et. al. ACS Catal. 2017, 7, 936; d) Ritter et. al. J. Am. Chem. Soc. 2012, 134, 12002.

Ni-salen complexes bearing pendant phenol groups in the secondary coordination sphere

Kaeden  Teindl
@KTeindl (https://twitter.com/KTeindl)
Undergraduate Student at University of the Fraser Valley, Abbotsford, Canada

Abstract:

The secondary coordination sphere (SCS) often plays an essential role in enzymatic processes [1], which has inspired efforts to integrate SCS design into synthetic targets [2-4]. To that end, this poster will discuss the synthesis and spectroscopic characterization of novel nickel-salen complexes with phenol moieties appended in their SCS [5]. Their electrochemical behaviors were probed by CV, and the subsequent one-electron oxidized species were prepared and investigated spectroscopically.

References, if applicable:

1. Jeoung, J.-H.; Dobbek, H. Science 2007, 318, 1461−1464
2. Sun, P; Yang, D; Li, Y; Wang, B; Qu, J. Dalton Trans. 2020, Advance Article
3. Hong, D; Kawanishi, T; Tsukakoshi, Y.; Kotani, H.; Ishizuka, T.; Kojima, T. J. Am. Chem. Soc. 2019, 141, 20309−20317
4. Wijeratne, G.B.; Bhadra, M.; Siegler, M.A.; Karlin, K.D. J. Am. Chem. Soc. 2019, 141, 17962−17967
5. Chiang et al. Chem. Eur. J. 2012, 18, 14117 – 14127

Structural Landscape of Lanthanide coordinated Anderson-Evans polyoxometalate

Shailabh  Tewari
@ShailabhTewari (https://twitter.com/ShailabhTewari)
Graduate Student at Indian Institute of Technology, Delhi, New Delhi, India

Arunachalam Ramanan, Indian Institute of Technology Delhi, India

Abstract:

The struggle in rationalizing crystallization, a supramolecular reaction, for the targeted design of functional materials is to recognize the underlined possible pathways. The task is significantly challenging due to the obscurity of well-defined links between synthesis, structure and property. However, Polyoxometalates (POM), the intermediate soluble molecular analogues of the bulk oxides, may provide some insights.

References, if applicable:

1. Tewari, S. et al. Front. Chem. 2019, 6, 635.

Gas phase characterization of a dinitrogen analogue of Zeise’s salt

Gilian  Thomas
@gilian_thomas (https://twitter.com/gilian_thomas)
Graduate Student at University of Victoria, Victoria, Canada

Sofia Donnecke, University of Victoria, Canada; Irina Paci, University of Victoria, Canada; Scott McIndoe, University of Victoria, Canada

Abstract:

We discovered a derivative of Zeise’s salt ([PtCl3(C2H4)]–), the [PtCl3(N2)]– complex spontaneously forms in the nitrogen-rich atmosphere of the mass spectrometer. Ion mobility separation of [PtCl3(C2H4)]–, [PtCl3(N2)]– and [PtCl3(CO)]–, and MS/MS experiments analyzed ligand binding strength for the isobaric complexes. These were in agreement with calculated values. Binding strength may allow [PtCl3(N2)]– to be isolated with the potential for dinitrogen functionalization and catalysis in water.

References, if applicable:

Impact of Sterics and Metal Choice on Isostructural Group VI Alkyne Metathesis Catalysts and the Selective Formation of Isomeric Metallacyclic Intermediates.

Richard R Thompson
@RichardRThomps1 (https://twitter.com/RichardRThomps1)
Post-doctoral Fellow at Louisiana State University, Baton Rouge, United States

Madeline Rotella, University of Maryland, USA; Frank Fronczek, Louisiana State University, USA; Osvaldo Gutierrez, University of Maryland, USA; Semin Lee, Louisiana State University, USA

Abstract:

Metallacyclobutadienes as part of a cycloaddition based mechanism for alkyne metathesis is an established paradigm with alternate species viewed as decomposition products. Recently we reported the exclusive formation of a dynamic metallatetrahedrane capable of metathesis raising question about the mechanism. Consequentially, we report the synthesis a library of both molybdenum and tungsten alkylidynes supported by sterically distinct ligands and the role metal identity has on intermediates.

References, if applicable:

Thompson, R. R.; Rotella, M. E.; Du, P.; Zhou, X.; Fronczek, F. R.; Kumar, R.; Gutierrez, O.; Lee, S., Siloxide Podand Ligand as a Scaffold for Molybdenum-Catalyzed Alkyne Metathesis and Isolation of a Dynamic Metallatetrahedrane Intermediate. Organometallics 2019, 38, 4054-4059.

Trans oxidative addition of arylfluorides to nickel N-heterocyclic carbene complexes

Adrian  Torres
@AdrianChem (https://twitter.com/AdrianChem)
Undergraduate Student at California State Polytechnic University, Pomona, Pomona, United States

Jacob P. Brannon, Masters Students, USA S. Chantal E. Stieber, Principal Investigator, USA

Abstract:

Nickel N-heterocyclic carbene (NHC) complexes with isopropyl groups were reported to yield trans addition of aryl fluorides. In this work, NHC ligands with methyl groups were studied for oxidative addition of aryl fluorides at nickel. The aryl fluoride nickel complex was obtained from an oxidative addition of hexafluorobenzene to the nickel(0) precursor. Complexes were characterized using NMR spectroscopy and X-ray crystallography. A trans addition product was observed for the methyl complex.

References, if applicable:

1)           Schaub, T.; Backes, M.; Radius, U. Square-Planar (Pentafluorophenyl)Nickel(II) Complexes by Derivatization of a C–F Activation Product. Eur. J. Inorg. Chem. 2008, 2008 (17), 2680–2690. https://doi.org/10.1002/ejic.200800213.

Clays modified with [Fe(o-phen)3]2+ complex for the removal of triclosan from aqueous solutions

Carlos Enrique Torres-Méndez
@randomrandom901 (https://twitter.com/randomrandom901)
Undergraduate Student at Escuela de Química, Facultad de Ciencias Químicas y Farmacia, Universidad de San Carlos de Guatemala, Guatemala, Guatemala

Dania Pérez-Fernández, Cristel Kim-Godoy, Christa Lemus-Lucas, Cesar A. Estrada, Silvia Echeverría, Escuela de Química, Facultad de Ciencias Químicas y Farmacia, Universidad de San Carlos de Guatemala, Guatemala

Abstract:

Bentonite (Bent) and vermiculite (Vrm) were modified by ionic exchange with [Fe(o-phen)3]SO4 complex. The modified clays showed a change of color to an intense red, characteristic of  [Fe(o-phen)3]2+ complex. Materials were characterized by ATR FTIR, the hybrid clays showed bands at 720, 848, 1428 cm-1 assigned to bending vibrations of C-H bonds in the aromatic rings of the o-phen ligand. Comparative analysis on isotherms and the sorption capacity of Bent, Verm and hybrid clays is presented.

References, if applicable:

(1)          Lei, C.; Hu, Y.; He, M. Adsorption Characteristics of Triclosan from Aqueous Solution onto Cetylpyridinium Bromide (CPB) Modified Zeolites. Chem. Eng. J. 2013, 219, 361–370.

(2)          Kabadagi, A.; Chikkamath, S.; Manjanna, J.; Kobayashi, S. In−situ Complexation of O−phenanthroline in the Interlayer of Fe(II)−montmorillonite. Appl. Clay Sci. 2018, 165, 148–154.

(3)          Foo, K. Y.; Hameed, B. H. Insights into the Modeling of Adsorption Isotherm Systems. Chem. Eng. J. 2010, 156 (1), 2–10.

(4)          Chen, X. Modeling of Experimental Adsorption Isotherm Data. Information 2015, 6 (1), 14–22.

Application of FLP Chemistry to Reactions with Bromoalkynes

Jonah  Toth
@jonahtoth (http://twitter.com/jonahtoth)
Undergraduate Student at University of Toronto, Toronto, Canada

Karlee L. Bamford, University of Toronto, Canada / Douglas W. Stephan, University of Toronto, Canada

Abstract:

It was previously reported that sterically encumbered or electron deficient phosphines do not react with (bromoethynyl)benzene.[1] Our work has involved a systematic study of the reactivity induced by Lewis acids of varied strength to promote reaction between haloalkynes of the form RCCBr and a range of phosphines bearing either bulky or electron-withdrawing substituents. This study represents the first known application of FLP chemistry involving bromoalkyne substrates.

References, if applicable:

[1] Veinot, A.J.; Todd, A.D.K.; Robertson, K.N.; Masuda, J.D. Can. J. Chem. 2017, 96, 8-17.

Development of Cu-pyridinedicarboxamide Complexes as C-H Bond Activation Reagents

Warren Ross VandeVen
@VandevenWarren (https://twitter.com/VandevenWarren)
Undergraduate Student at University of the Fraser Valley, Abbotsford, Canada

Abstract:

Nature utilizes high valent metal centers in enzymes to functionalize relatively inert C-H bonds.1-2 Synthetic Cu(III) complexes, ligated by a dianionic, tridentate pyridinedicarboxamide (PCA) ligand, have demonstrated success in such reactions.3-4 This poster will discuss the synthesis and characterization of a Cu complex ligated by an electron-rich PCA ligand. A more electron donating ligand is expected to stabilize the Cu(III) metal center, improving C-H bond activation reactivity.

References, if applicable:

1. Nam, W. Acc. Chem. Res. 2007, 40, 522.
2. Latham, J.; Brandenburger, E.; Shepherd, S. A.; Menon, B. R. K.; Micklefield, J. Chem. Rev. 2018, 118, 232.
3. Donoghue, P. J.; Tehranchi, J.; Cramer, C. J.; Sarangi, R.; Solomon, E. I.; Tolman, W. B. J. Am. Chem. Soc. 2011, 133, 17602.
4. Bower, J.K., Cypcar, A.D., Henriquez, B., Chantal, S., Stieber, E., Zhang, S., J. Am. Chem. Soc. 2020, 142, 8514.

The path from darkness to light: octahedral iridium(III) complexes to combat cancer.

Gloria  Vigueras
@ViguerasGloria (https://twitter.com/ViguerasGloria)
Graduate Student at University of Murcia, Murcia, Spain

Natalia Cutillas, Faculty of chemistry, University of Murcia, Spain. José Ruiz, Faculty of chemistry, University of Murcia, Spain. Vojtech Novohradsky, Institute of Biophysics, Academy of Sciences of the Czech Republic, Czech Republic.Jana Kasparkova, Institute of Biophysics, Academy of Sciences of the Czech Republic, Czech Republic. Viktor Brabec. Institute of Biophysics, Academy of Sciences of the Czech Republic, Czech Republic.

Abstract:

We will present our recent results on the synthesis and biological evaluation of different bis-cyclometalated Ir(III) complexes.[1-3] Modifying the cyclometalated ligand and/or ancillary ligand we can tuned their antitumoral activity. Thus, some of them are very active in several cancer cell lines in the dark while others, are able to activate by irradiation with visible light.

References, if applicable:

1. Yellol, J.; Pérez, S. A.; Yellol, G.; Zajac, J.; Donaire, A.; Vigueras, G.; Novohradsky, V.; Janiak, C.; Brabec, V.; Ruiz, J. Chem. Commun. 2016, 52, 14165.
2. Pracharova, J.; Vigueras, G.; Novohradsky, V.; Cutillas, N.; Janiak, C.; Kostrhunova, H.; Kasparkova, J.; Ruiz, J.; Brabec, V. Chemistry 2018, 24, 4607.
3. Novohradsky, V.; Vigueras, G.; Pracharova, J.; Cutillas, N.; Janiak, C.; Kostrhunova, H.; Brabec, V.; Ruiz, J.; Kasparkova, J. Inorg. Chem. Front. 2019, 6, 2500.

INVESTIGATIONS INTO THE POLYMERIZATION MECHANISM AND REACTIVITY OF 1-PHOSPHABUTADIENES

Henry  Walsgrove
@HWalsgrove (https://mobile.twitter.com/HWalsgrove)
Graduate Student at University of British Columbia, Vancouver, Canada

Derek Gates

Abstract:

We recently reported the polymerization of 1-phosphaisoprene by anionic initiation.[1] Studies of the polymer microstructure showed predominantly 3,4-addition across the C=C double bond, forming a polymer containing pendant phosphaalkene groups. Initiation studies using nBuLi show a 4,1-enchainment, in contrast to the proposed polymer microstructure resulting from 4,3-addition. Further investigation of the reactivity of 1-phosphabutadiene species will also be presented.[2,3]

References, if applicable:

1. Dück, K.; Rawe, B. W.; Scott, M. R.; Gates, D. P. Angew. Chem. Int. Ed. 2017, 56, 9507.
2. Ohtsuki, K.; Walsgrove, H. T. G.; Hayahsi, Y.; Kawauchi, S.; Patrick, B. O.; Gates, D. P.; Ito, S. Chem. Commun. 2020, 56, 774.
3. Walsgrove, H. T. G.; Dabringhaus, P.; Patrick, B. O.; Gates, D. P. Can. J. Chem. 2020, 98, 373.

Supramolecular Capsules from Iso-Chalcogenazole N-Oxides

JinZhao  Wang
@zoomjin19 (https://twitter.com/zoomjin19)
Graduate Student at McMaster University, Hamilton, Canada

Peter C. Ho, and Ignacio Vargas-Baca

Abstract:

Amongst the many molecules that are capable of forming chalcogen bonds, iso-tellurazole N-oxides stand out because of their ability to reversibly form macrocyclic aggregates that are persistent in solution [1,2]. In recent investigations, we have found a procedure that builds a dodecamer that folds onto itself forming a cavitand that encapsulates certain molecules such as cyclohexane, tetrahydrofuran and dioxane.

References, if applicable:

1. P.C. Ho, P. Szydlowski, J. Sinclair, P. J. W. Elder, J. Kübel, C. Gendy, L. Myongwon Lee, H. Jenkins, J. F. Britten, D. R. Morim, I. Vargas-Baca. Nature Commun. 2016, 7:11299.
2. P.C. Ho, J. Rafique, L. M. Lee, H. A. Jenkins, J. F. Britten, A. L. Braga, I. Vargas-Baca.* Dalton Trans., 2017, 46, 6570-6579.

Oxidative addition reactions of tetrathiocins to group 10 metals: From structural diversity to sensor development.

Lara K Watanabe
@larawatanabe (https://twitter.com/larawatanabe)
Graduate Student at University of Windsor, Windsor, Canada

Justin D. Wrixon, University of Windsor, Canada, Zeinab S. Ahmed, University of Windsor, Canada, John J. Hayward, University of Windsor, Canada, Parisa Abbasi, Brock University, Canada, Melanie Pilkington, University of Windsor, Canada, Charles L. B. Macdonald, Carleton University, Canada, and Jeremy M. Rawson, University of Windsor, Canada

Abstract:

Metal dithiolene complexes are ideal for various materials applications. Oxidative addition reactions of bis(benzo)-1,2,5,6-tetrathiocins to zero valent group 10 metal complexes leads to mono-, di- and hexa-nuclear complexes depending on the steric effects of the phosphine. We have exploited this synthetic methodology to provide a simple two-step route to functionalized dithiolate complexes that we can explore as sensors for Na+ cations.

References, if applicable:

1. Dithiolene chemistry: Synthesis, properties, and applications, ed. E. I. Stiefel, Interscience, Hoboken, New Jersey, 2003.
2. Wrixon, J.; Hayward, J.; Raza, O.; and Rawson, J. M., Dalton Trans. 2014, 43, 2134.
3. (a) Wrixon, J.; Hayward, J.; and Rawson, J. M., Inorg. Chem., 2015, 54, 9384-9386; (b) Wrixon, J.; Ahmed, Z. S.; Anwar, M. U.; Beldjoudi, Y.; Hamidouche, N.; Hayward J. J.; and Rawson, J. M., Polyhedron, 2016, 108, 115-121.
4. Watanabe, L. K.; Wrixon, J. D.; Ahmed, Z. S.; Hayward, J. J.; Abbasi, P.; Pilkington, M.; Macdonald, C. L. B., and Rawson, J. M., Dalton Trans., 2020, DOI: 10.1039/D0DT01678K.

Synthesis, characterization and cytotoxicity studies of multinuclear benzimidazole-based cyclometallated and cationic ruthenium(II) complexes

Athi  Welsh
@athiwelsh (https://twitter.com/athiwelsh)
Graduate Student at Chemistry, Cape Town, South Africa

Sharon Prince and Gregory S. Smith

Abstract:

In this study, a series of trimeric benzimidazole ligands, and their respective trinuclear Ru(II) complexes were synthesized and screened for their anticancer activity against two breast cancer cell lines. Overall, the compounds show anticancer activity either comparable to or greater than that of cisplatin. Importantly, the compounds have relatively low toxicity towards the non-tumorigenic cells and were noted to be significantly more selective for breast cancer cells compared to cisplatin.

References, if applicable:

1. A. Welsh, L. Rylands, V. B. Arion, S. Prince and G. S. Smith, Dalton Trans., 2020, 49, 1143 – 1156.

Examination of the Effects of Solvents on Homogeneous CO2 Reduction Electrocatalysis

Lucienna M Wolf
@LucyWol58238133 (https://twitter.com/LucyWol58238133)
Undergraduate Student at DePaul University, Chicago, United States

Kyle A. Grice, DePaul University, United States

Abstract:

Significant effort has been focused on designing more efficient catalysts for CO2 reduction, yet there is minimal information regarding the effects of solvent environments on these systems.  Electrochemical and spectroscopic data collected from experiments using the canonical fac-Re(bpy)(CO)3Cl electrocatalyst in various solvents were compared to the solvents’ physical properties and their economic and environmental properties to determine the most optimal conditions for CO2 reduction systems.

References, if applicable:

1. Blunden, J., D. S. Arndt, and G. Hartfield , Eds., 2018: State of the Climate in 2017. Bull. Amer. Meteor. Soc., 99 (8), Si–S310, doi:10.1175/2018BAMSStateoftheClimate.1.
2. Lu, Q.; Jiao, F., Electrochemical CO2 reduction: Electrocatalyst, reaction mechanism, and process engineering. 2016; Vol. 29.
3. Grice, K. A.; Saucedo, C., Electrocatalytic Reduction of CO2 by Group 6 M(CO)6 Species without “Non-Innocent” Ligands. Inorganic Chemistry 2016, 55, 6240-6246.
4. Bron, M., Infrared Spectroelectrochemistry. In Encyclopedia of Applied Electrochemistry, Kreysa, G.; Ota, K.-i.; Savinell, R. F., Eds. Springer. New York: New York, NY, 2014; pp 1071-1075.
5. Gutmann, V. (1978)The donor-acceptor aproach to molecular interactions. New York: Plenum Press.
6. Dean, J. A.; Lange, N. A., Lange’s handbook of chemistry. 15th ed. ed.; McGraw-Hill: New York, 1999.

Mechanistic Studies into Iron-Catalysed Alkene Isomerisation

Callum R Woof
@Callum_Woof (https://twitter.com/Callum_Woof)
Graduate Student at University of Bath, Bath, United Kingdom

Derek J Durand, University of Bristol, UK, Craig P Butts, University of Bristol, UK, Natalie Fey, University of Bristol, UK, Emma Richards, Cardiff University, UK, Ruth L Webster, University of Bath, UK

Abstract:

We have investigated the catalytic isomerisation of alkenes using a ß-diketiminate iron(II) complex and a hydride source. Whilst we initially hypothesised this to be an entirely redox-neutral process in line with similar transformations [1,2], upon studying the reaction further with a broad range of techniques including synthetic, EPR and electrochemical studies we now believe that the active species is an Fe(I) complex forming in situ, and the reaction proceeds by a redox-active pathway.

References, if applicable:

[1] M. Espinal-Viguri, R. L. Webster et.al., Chem. Eur. J., 2016, 22, 11605

[2] M. Espinal-Viguri, R. L. Webster et.al., J. Am. Chem. Soc., 2019, 141, 572

Rational design and synthesis of near-infrared phthalocyanine-based absorbing

Aymen N Yaseen
@AymenNYaseen (https://twitter.com/AymenNYaseen)
Graduate Student at Gebze Technical University, Kocaeli, Turkey

1) Ayşe Gül Gürek, Gebze Technical University, Chemistry Department, Gebze, Kocaeli, Turkey   2) Fabienne Dumoulin

Abstract:

Photosensitizers for photodynamic therapy must ideally be excited by NIR wavelengths to reach deep-seated tumors (1). Phthalocyanines are very suitable as their max. absorption can be tuned from 680 to 800 nm (2,3). To benefit from the tumor-targeting Enhanced Permeation and Retention effect (4,5), organosilica nanoparticles are aimed to be prepared from phthalocyanines absorbing at 800 nm. A careful design and synthetic strategy of appropriately functionalized phthalocyanines will be presented.

References, if applicable:

(1)          Mallidi, S.; Anbil, S.; Bulin, A. L.; Obaid, G.; Ichikawa, M.; Hasan, T. Theranostics 2016, 6 (13), 2458–2487.

(2) Lo, P. C.; Rodríguez-Morgade, M. S.; Pandey, R. K.; Ng, D. K. P.; Torres, T.; Dumoulin, F.  Chem. Soc. Rev. 2020, 49 (4), 1041–1056.

(3)          Topal, S. Z.; İşci, Ü.; Kumru, U.; Atilla, D.; Gürek, A. G.; Hirel, C.; Durmuş, M.; Tommasino, J.-B.; Luneau, D.; Berber, S.; Dumoulin, F.; Ahsen, V. Dalt. Trans. 2014, 43 (18), 6897–6908

(4)          Maeda, H.; Nakamura, H.; Fang, J. Adv. Drug Deliv. Rev. 2013, 65 (1), 71–79.

(5)          Maeda, H.; Tsukigawa, K.; Fang, J. Microcirculation 2016, 23 (3), 173–182.

Synthesis of Nickel Nitrosyl Complexes with Bidentate N-heterocyclic Carbene Ligands

Zijie  Zhang
@zhang_zijie (https://twitter.com/zhang_zijie)
Undergraduate Student at California State Polytechnic University, Pomona, Pomona, United States

1. Chantal E. Stieber, California State Polytechnic University, Pomona, United States

Abstract:

Activation of small molecules like NO offer insight towards biological reduction mechanisms. Nickel nitrosyl complexes were synthesized to examine the effect of NHC ligands on the nickel-NO bond. A new metal complex (MesNHC2Me)Ni(COD) was synthesized and structurally characterized. A new Ni-NO complex [(MesNHC2Me)Ni(NO)][BF4] was synthesized and characterized by IR spectroscopy, which is a new example of a three-coordinate nickel nitrosyl complex with strongly sigma donating ligands.

References, if applicable:

1. Nolan, S. N-Heterocyclic Carbenes: Effective Tools for Organometallic Synthesis. 2014.
2. Hermann, W.A. et al. J. Organomet.Chem. 1999, 572, 239.
3. Liu, J.; Chen, J.; Zhao, J.; Zhao, Y.; Li, L.; Zhang, H. Synthesis, 2003, 17, 2661–2666.
4. Cowie, M.; Wells, K. D.; Ferguson, M. J.; Mcdonald, R. Organometallics, 2008, 27(4), 691–703.
5. Yamamoto, C. D.; Zhang, Z.; Stieber, S. C. E. Acta Crystallogr. Sect. E Crystallogr. Commun. 2018, 74 (10), 1396–1399.
6. Wright, A. M.; Zaman, H. T.; Wu, G.; Hayton, T. W. Inorg. Chem. 2014, 53 (6), 3108–3116
7. Tskhovrebov, A. G.; Solari, E.; Scopelliti, R.; Severin, K. Inorg. Chem. 2013, 52 (20), 11688–11690
8. Chattopadhyay, T.; Podder, N.; Banu, K. S.; Banerjee, A.; Ghosh, M.; Suresh, E.; Nethaji, M.; Das, D. J. Mol. Struct. 2007, 839 (1–3), 69–75.
9. Golchoubian, H.; Kocheksaraee, S. K.; Moayyedi, G. Polyhedron 2017, 123 (2), 376–384.
10. Meidine, M. F.; Pombeiro, A. J. L.; Nixon, J. F. 1999, 839, 3041–3045.

Organotin(IV) Complexes as Catalyst for Biodiesel Formation: Synthesis, Structural Elucidation and Computational Studies

Muhammad  Zubair
@zubairmarwatqau (https://twitter.com/zubairmarwatqau)
Graduate Student at Quaid-i-azam university Islamabad, Islamabad, Pakistan

Ali Haidera*, Muhammad Sirajuddinb, Ishtiaq Hussainc, Muhammad Nawaz Tahird, Saqib Alia*

Abstract:

Here we have presented the synthesis of three novel triorganotin(IV) complexes. Spectroscopically characterized by NMR in solution and by FT-IR, X-ray diffraction analysis in solid state. The computational study was also performed . The homogeneous catalytic performance was evaluated for the transesterification of corn oil with methanol into biodiesel. The catalytic results revealed that the complexes are potential candidates for the development of new catalytic system for biodiesel production.

References, if applicable:

Muhammad Zubair.  Appl. Organomet. Chem. 2020, 34, e5305